polymeric acid catalysts and their uses

专利摘要:
POLYMERIC ACID CATALYSTS AND THEIR USES. Polymers useful as catalysts in non-enzymatic saccharification processes are provided. Methods are also provided for the hydrolysis of cellulosic materials into monosaccharides and / or oligosaccharides using these polymeric acid catalysts
公开号:BR112013022047B1
申请号:R112013022047-3
申请日:2012-02-27
公开日:2020-11-17
发明作者:Ashish Dhawan；Brian M. Baynes；John M. Geremia
申请人:Cadena Bio, Inc；
IPC主号:

专利说明:

Cross Reference for Related Orders
[0001] This application claims priority for U.S. Provisional Patent Application No. US 61 / 447,311 filed on February 28, 2011, and US Provisional Patent Application No. US 61 / 522,351 filed on February 11, 2011. August 2011, each of which is incorporated herein by reference in its entirety. Field of the Invention
[0002] The present invention relates, in general, to catalysts that can be used in biomass saccharification, and, more specifically, to polymeric acid catalysts that can be used to hydrolyze cellulose and / or hemicellulose. Background of the Invention
[0003] Saccharification of cellulosic materials, especially biomass residues from agriculture, forestry and waste treatment are of great economic and environmental relevance. As part of the use of biomass energy, attempts were made to obtain ethanol (ethanol) by cellulose hydrolysis or hemicellulose, which are the main constituents of plants. Hydrolysis products, which include sugars and simple carbohydrates, can then be subjected to further biological and / or chemical conversion to produce fuels or other basic chemicals. For example, ethanol is used as a fuel or mixed with a fuel, such as gasoline. The main constituents of plants include, for example, cellulose (a glucose polymer, which is a six-carbon sugar), hemicellulose (a branched polymer of five and six carbons), lignin and starch. Current methods for releasing sugars from lignocellulosic materials, however, are inefficient on a commercial scale based on yield, as well as water and energy used.
[0004] The 1980s work on the hydrolysis of β-glycosidic bonds using super-acidic perfluoronated microporous resins, such as Dupont Nafion®, attempted to develop catalytic methods for use in digesting cellulose. Discontinuous reactors and continuous flow reactors of fixed tube beds were used to demonstrate the hydrolysis of celooligosaccharides to monomeric sugars; However, these processes have not been able to achieve appreciable digestion of cellulose or hemicellulose, and in particular, the crystalline areas of cellulose.
[0005] As such, there is an ongoing need for new catalysts that can efficiently generate sugar and sugar-containing products from biomass on a commercially viable scale. Summary of the Invention
[0006] The present invention addresses this need by providing polymeric materials that can be used to digest hemicellulose and cellulose, including crystalline cellulose domains, in biomass. Specifically, polymeric materials can hydrolyze cellulose and / or hemicellulose into monosaccharides and / or oligosaccharides.
[0007] In one aspect, a polymer is provided that has acidic monomers and ionic monomers that are linked to form a polymeric backbone, where each acidic monomer has at least one Bronsted-Lowry acid, and each ionic monomer has, independently at least one nitrogen-containing cationic group or phosphorus-containing cationic group. In some embodiments, each acid monomer has a Bronsted-Lowry acid. In other embodiments, some of the acidic monomers have a Bronsted-Lowry acid, while others have two Bronsted-Lowry acids. In some embodiments, each ionic monomer has a nitrogen-containing cationic group or phosphorus-containing cationic group. In other embodiments, some of the ionic monomers have a nitrogen-containing cationic group or phosphorus-containing cationic group, while others have two nitrogen-containing cationic groups or phosphorus-containing cationic groups.
[0008] In some embodiments, Bronsted-Lowry acid, in each occurrence, is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluoric acid. In certain embodiments, Bronsted-Lowry acid, in each occurrence, is, independently, sulfonic acid or phosphonic acid. In one embodiment, Bronsted-Lowry acid, in each occurrence, is sulfonic acid.
[0009] In some embodiments, the one or more of the acidic monomers are directly linked to the polymer chain. In other embodiments, the one or more of the acidic monomers further includes a linker that binds Bronsted-Lowry acid to the polymeric backbone. In certain embodiments, some of the Bronsted-Lowry acids are directly linked to the polymeric backbone, while other Bronsted-Lowry acids are linked to the polymeric backbone via a linker.
[0010] In these embodiments, where Bronsted-Lowry acid is linked to the polymeric backbone via a linker, the linker at each occurrence is independently selected from unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, substituted alkenylene or unsubstituted, unsubstituted or substituted arylene, substituted or unsubstituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate. In certain embodiments, the binder is unsubstituted or substituted arylene, substituted or unsubstituted heteroarylene. In certain embodiments, the binder is unsubstituted or substituted arylene. In one embodiment, the binder is phenylene. In another embodiment, the linker is hydroxyl substituted phenylene.
[0011] In these embodiments, where Bronsted-Lowry acid is linked to the polymeric backbone, via a linker, Bronsted-Lowry acid and the linker form a side chain. In some embodiments, each side chain can be independently selected from:


[0012] In some embodiments, the cationic group containing nitrogen, in each occurrence, is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, piradizimio, tiazinio, morfolinio, piperidinio, piperizinio, and pirollizinio. In one embodiment, the nitrogen-containing cationic group is imidazolium.
[0013] In some embodiments, the cationic group containing phosphorus in each occurrence is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichlor phosphonium, and trifluoro phosphonium. In one embodiment, the phosphorus-containing cationic group is triphenyl phosphonium.
[0014] In some embodiments, the one or more of the ionic monomers are directly linked to the polymeric chain. In other embodiments, the one or more of the ionic monomers each further includes a linker that binds the nitrogen-containing cationic group or the phosphorus-containing cationic group to the polymeric backbone. In certain embodiments, some of the cationic groups are directly linked to the polymeric backbone, while other cationic groups are linked to the polymeric backbone through a linker.
[0015] In these embodiments, in which the nitrogen-containing cationic group is linked to the polymeric skeleton through a ligand, the nitrogen-containing cationic group and the ligand form a side chain. In some embodiments, each side chain independently, selected from:




[0016] In these embodiments, in which the phosphorus-containing cationic group is linked to the polymeric skeleton, through a linker, the phosphorus-containing cationic group and the side chain ligand is independently selected from:

[0017] In these embodiments, in which the cationic group is linked to the polymeric skeleton, through a linker, the linker in each occurrence is independently selected from unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, substituted or substituted alkenylene unsubstituted, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate. In certain embodiments, the binder is unsubstituted or substituted arylene, substituted or unsubstituted heteroarylene. In replaced. In one embodiment, the binder is phenylene. In another embodiment, the linker is substituted phenylene hydroxyl.
[0018] In some embodiments, the polymeric structure is selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly (acrylonitrile-butadiene). ).
[0019] In certain embodiments, the polymeric structure is polyethylene or polypropylene. In one embodiment, the polymeric backbone is polyethylene. In another, the polymeric skeleton is polyvinyl alcohol. In yet another embodiment, the polymeric structure is polystyrene.
[0020] In other embodiments, the polymer backbone is selected from polialquilenoamônio, polialquilenodiamônio, polialquilenopirrolio, polialquilenoimidazolio, polialquilenopirazolium, polialquilenooxazolium, polialquilenotiazolio, polialquilenopiridinium, polialquilenopirimidinium, polialquilenopirazinium, polialquilenopiradizimium, polialquilenotiazinium, polialquilenomorfolinium, polialquilenopiperidinium, polialquilenopiperizinium, polialquilenopirollizinium, polialquilenotrifenilfosfônio, polialquilenotrimetilfosfônio , polyalkylenetriethylphosphonium, polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium, polyalkylenetrichlorophosphonium, polyalkylenetrifluorophosphonium and polyalkylenediazole.
[0021] In other embodiments, the polymeric structure is alkyleneimidazole, which refers to an alkylene radical, in which one or more of the methylene units of the alkylene moiety has been replaced with imidazolium. In one embodiment, the polymeric structure is polyethyleneimidazole, polypropyleneimidazole, polybutyleneimidazole. In addition, it should be understood that, in other embodiments of the polymeric backbone, when a cationic group containing nitrogen or a cationic group containing phosphorus follows the term "alkylene", one or more of the methylene units of the alkylene portion is replaced with which group special nitrogen-containing cationic or phosphorus-containing cationic group.
[0022] In some embodiments, the polymer is cross-linked. In certain embodiments, at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 99% of the polymer is cross-linked.
[0023] In some embodiments, acidic monomers and ionic monomers are randomly arranged in an alternating sequence. In other embodiments, acidic monomers and ionic monomers are arranged in blocks of monomers. In certain embodiments in which acidic monomers and ionic monomers are arranged in blocks of monomers, each block has no more than 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4 or 3 monomers.
[0024] In some embodiments, the polymer further includes hydrophobic monomers attached to the polymeric backbone, where each hydrophobic monomer has a hydrophobic group. In some embodiments, the hydrophobic group at each occurrence is independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, or an unsubstituted or substituted heteroaryl. In certain embodiments, the hydrophobic group is at each occurrence an unsubstituted or substituted aryl group, or an unsubstituted or substituted heteroaryl group. In one embodiment, the hydrophobic group at each occurrence is phenyl.
[0025] In some embodiments, the hydrophobic group is directly linked to the polymeric backbone.
[0026] In some embodiments, the polymer further includes acid-ionic monomers attached to the polymeric backbone, in which each acid-ionic monomer has a Bronsted-Lowry acid and a cationic group. In some embodiments, the cationic group is a cationic group containing nitrogen or a cationic group containing phosphorus.
[0027] In certain embodiments, Bronsted-Lowry acid, at each occurrence in the acid-ionic monomer, is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluoric acid. In certain embodiments, Bronsted-Lowry acid, in each occurrence, is, independently, sulfonic acid or phosphonic acid. In one embodiment, Bronsted-Lowry acid, in each occurrence is sulfonic acid
[0028] In some embodiments, the nitrogen-containing cationic group, at each occurrence in the acid-ionic monomer, is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, piradizimio, thiazinium, morpholinium , piperidinium, piperizinium, and pyrollizinium. In one embodiment, the nitrogen-containing cationic group is imidazolium.
[0029] In some embodiments, the cationic group containing phosphorus, in each occurrence in the acid-ionic monomer, is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichlor phosphonium, and trifluoro phosphonium. In one embodiment, the phosphorus-containing cationic group is triphenyl phosphonium.
[0030] In some embodiments, the one or more of the ionic acid monomers each includes more than one ligand that binds Bronsted-Lowry acid or the cationic group to the polymeric backbone. In these embodiments, where Bronsted-Lowry acid or the cationic group is attached to the polymeric backbone through a linker in the acid-ionic monomer, the linker in each occurrence is independently selected from unsubstituted or substituted alkylene, cycloalkylene not substituted or substituted, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, substituted or unsubstituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate. In certain embodiments, the binder is unsubstituted or substituted arylene, substituted or unsubstituted heteroarylene. In certain embodiments, the binder is unsubstituted or substituted arylene. In one embodiment, the binder is phenylene. In another embodiment, the binder is hydroxy substituted phenylene.
[0031] In these embodiments, where Bronsted-Lowry acid and / or the cationic group of the acid-ionic monomer are linked to the polymeric backbone through a ligand, Bronsted-Lowry acid and / or the cationic group and the ligand form a side chain of the acid-ionic monomer. In some embodiments, each side chain of the acid-ionic monomer can be independently selected from:


[0032] In some embodiments, the polymer has a total amount of Bronsted-Lowry acid of between 0.1 and 20 mmol, between 0.1 and 15 mmol, between 0.01 and 12 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol, between 2 and 7 mmol, between 3 and 6 mmol, between 1 and 5, or between 3 and 5 mmol per gram of polymer.
[0033] In some embodiments, at least a portion of the acid monomers have sulfonic acid. In embodiments in at least a portion of the acid monomers have sulfonic acid, the total amount of sulfonic acid in the polymer is between 0.05 and 10 mmol, between 1 and 8 mmol, or between 2 and 6 mmol per gram of polymer.
[0034] In some embodiments, at least a portion of the acid monomers have phosphonic acid. In these embodiments where at least a portion of the acidic monomers have phosphonic acid, where the polymer, the total amount of phosphonic acid, where the polymer is between 0.01 and 12 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol, 2 or between and 6 mmol per gram of polymer.
[0035] In some embodiments, at least a portion of the acid monomers have acetic acid. In embodiments in at least a portion of the acid monomers have acetic acid, the total amount of acetic acid, where the polymer is between 0.01 and 12 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol , or between 2 and 6 mmol per gram of polymer.
[0036] In some embodiments, at least a portion of the acid monomers have isophthalic acid. In embodiments in at least a portion of the acid monomers have isophthalic acid, the total amount of isophthalic acid is the polymer between 0.01 and 5 mmol, between 0.05 and 5 mmol, between 1 and 4 mmol, or between 2 and 3 mmol per gram of polymer.
[0037] In some embodiments, at least a portion of the acid monomers have boronic acid. In embodiments in at least a portion of the acidic monomers have boronic acid, the total amount of boronic acid in the polymer is between 0.01 and 20 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol, or between 2 and 6 mmol per gram of polymer.
[0038] In some embodiments, at least a portion of the acid monomers have perfluoric acid. In embodiments in at least a portion of the perfluorinated acid monomers have acid, the total amount of perfluoric acid in the polymer is between 0.01 and 5 mmol, between 0.05 and 5 mmol, between 1 and 4 mmol, or between 2 and 3 mmol per gram of polymer.
[0039] In some embodiments, each ionic monomer also includes a cationic counterion for each group containing nitrogen or the cationic group containing phosphorus. In certain embodiments, the counter-ion at each occurrence is independently selected from halide, nitrate, sulfate, formate, acetate, or organo-sulfonate. In some embodiments, the counterion is fluoride, chloride, bromide, or iodide. In one embodiment, the counterion is chloride. In another embodiment, the counter-ion is sulfate. In yet another embodiment, the counterion is ethyl.
[0040] In some embodiments, the polymer has a total amount of cationic groups and counterions containing nitrogen or a total amount of phosphorus containing cationic groups and counterions of between 0.01 and 10 mmol, between 0.05 and 10 mmol, between 1 and 8 mmol, between 2 and 6 mmol, or between 3 and 5 mmol per gram of polymer.
[0041] In some embodiments, at least a portion of the ionic monomers have imidazolium. In embodiments in at least a portion of the ionic monomers have imidazolium, the total amount of imidazolium and counterions where the polymer is between 0.01 and 8 mmol, between 0.05 and 8 mmol, between 1 and 6 mmol , or between 2 and 5 mmol per gram of polymer.
[0042] In some embodiments, at least a portion of the ionic monomers have pyridinium. In embodiments in at least a portion of th ionic monomers have pyridinium, the total amount of pyridinium and counterions in which the polymer is between 0.01 and 8 mmol, between 0.05 and 8 mmol, between 1 and 6 mmol, or between 2 and 5 mmol per gram of polymer.
[0043] In some embodiments, at least a portion of the ionic monomers have triphenyl phosphonium. In embodiments in at least a portion of the ionic monomers have triphenyl phosphonium, the total amount of triphenyl phosphonium and counterions in which the polymer is between 0.01 and 5 mmol, between 0.05 and 5 mmol, between 1 and 4 mmol, or between 2 and 3 mmol per gram of polymer.
[0044] Since they are also polymers selected from: poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazol-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3 / 1-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3 / 7-imidazole-1-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-iodide-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-bromide-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3 / 1-benzoimidazole-1-formate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-chloride-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; (4-vinylbenzyl) -pyridine-bromide-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazol-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-iodide-co-3-methyl-l- (4-vinylbenzyl) - 3 // - imidazole-bisulfate-co- divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-bisulfate-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-acetate-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-formate-co-divinylbenzene]; triphenyl- (4-vinylbenzyl) -phosphono chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triphenyl- (4-vinylbenzyl) -phosphono bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic -co-triphenyl- (4-vinylbenzyl) -phosphono acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1-methyl-1- (4-vinylbenzyl) -pipererdin-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1-methyl-1- (4-vinylbenzyl) -pipererdin-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1-methyl-1- (4-vinylbenzyl) -pipererdin-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4- (4-vinylbenzyl) -morpholinae-4-oxide-co-divinyl benzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium acetate-co-divinylbenzene]; 1-chloride-co-4-boronyl-1- (4-vinylbenzyl) -pyridine chloride-co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-1- (4-vinylphenyl) methylphosphonic acid -co- divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-1- (4-vinylphenyl) methylphosphonic acid -co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-1- (4-vinylphenyl) methylphosphonic acid -co- divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-nitrate-co-1- (4-vinylphenyl) methylphosphonic acid -co- divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-viniIbenziIchloride-co-1-methyl-2-vinyl-pyridine chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine acetate-co-divinylbenzene]; (4-vinylbenzyl) -morpholinae-4-oxide-co-divinyl benzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) -isophthalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) - isofithalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) - isofithalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co- 3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co- 3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co- 3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole chloride-co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenyl phosphone chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole chloride-co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenyl phosphone chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole bisulfate-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole acetate-co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenyl phosphone acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole acetate-co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenyl phosphone acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine acetate-co vin ylbenzyltriphenyphosphone bisulfate-co-divinylbenzene) poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole chloride-co-divinyl) chloride; poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole nitrate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (butyl-viniliinidazole chloride-co-butylimidazole bisulfate-co-4-vinylbenzenesulfonic acid); poly (butyl vinylimidazole bisulfate-co-butylimidazole bisulfate-co-4-vinylbenzenesulfonic acid); poly (benzyl acid alcohol-co-4-vinylbenzyl alcohol sulfonic -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzyl alcohol); and poly (benzyl acid alcohol-co-4-vinylbenzyl alcohol sulfonic -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzyl alcohol).
[0045] In some embodiments, the polymer is: poly-styrene-co-4-vinylbenzenesulfonic acid-3-methyl-1 - (4-vinylbenzyl) -3H-imidazol-1-yo-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid-3-methyl-1 - (4-vinylbenzyl) -3H-imidazole-1-chloro-codivinylbenzene]; or methyl-1 - (4-vinylbenzyl) -3H-imidazole-1-ethyl — a codivinylbenzene].
[0046] In other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic acid-3-ethyl-1- (4-vinylbenzyl) -3H-imidazol-1-yo-bisulfate codivinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic lactic-co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloro-codivinylbenzene]. poly [styrene-co-4-vinylbenzenesulfonic acid co-1- (4-vinylbenzyl) -3H-imidazole-1-yo bisulfate-co-divinylbenzene]; or poly [styrene-co-4-vinylbenzenesulfonic acid-3-methyl-1 - (4-vinylbenzyl) -3H-benzoimidazole-1-yo-bisulfate codivinylbenzene].
[0047] In other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic lactic-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-a chloro-codivinylbenzene].
[0048] In other embodiments, the polymer is: poly [styrene-co-4-vinylphenylphosphonic acid-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-yo-codivinylbenzene]; or poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-io-col-chloride (4-vinylphenyl) methyl-f-acid, codivinylbenzene].
[0049] In other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic 1- acid-co (4-vinylbenzyl) -pyridinium-bisulfate-codivinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic co-acid 1- (4-vinylbenzyl) -pyridiniumchloro-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-io-bisulfate codivinylbenzene]; or poly [styrene-co-4-vinylbenzenesulfonic-co-vinylbenzylchloro-co-1-methyl-2-vinyl-pyridinium chloro-codivinylbenzene].
[0050] In still other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic-co-acid 4-methyl-4- (4-vinylbenzyl) -morpholin-4-io-bisulfate codivinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic-co-acid 4- (4-vinylbenzyl) -morpholine benzene-co-divinyl]; or poly [styrene-co-4-vinylbenzenesulfonic-co-acid 4- (4-vinylbenzyl) -morpholine-4-oxide-codivinyl benzene].
[0051] In still other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic-co-triphenyl (4-vinylbenzyl) -phosphonium bisulfate-
[0052] In still other embodiments, the polinmer is: poly [styrene-co-4-vinylbenzenesulfonic co-acid 1- (4-vinylbenzyl) -piperidine-co-divinylbenzene]; or poly [styrene-co-4-vinylbenzenesulfonic-lactic-co-1 methyl-1- (4-vinylbenzyl) -perderd-1-io-codivinyl benzene chloride].
[0053] In still other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic-co-triethyl- (4-vinylbenzyl) - ammonium chloride-codivinylbenzene].
[0054] In still other embodiments, the polymer is: poly [styrene-co-4-vinylbenzenesulfonic-co-acid 4- (4-vinylbenzyl) -morpholine-4-oxide-codivinyl benzene].
[0055] In still other embodiments, the polymer is: poly [styrene-co-5- (4-vinylbenzylamino) lactic isophthalic-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chlorine - codivinylbenzene].
[0056] In still other embodiments, the polymer is: poly [styrene-CO- (4-vinylbenzylamino) -acetic acid-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-a chlorine- codivinylbenzene].
[0057] In some embodiments, the polymer is: poly (styrene-co-4-vinylbenzenesulfonic-co-acid vinylbenzyylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene); or poly (styrene-co-4-vinylbenzenesulfonic-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene).
[0058] In other embodiments, the polymer is: poly (benzyl alcohol co-4-sulfonic acid vinylbenzylalcohol-co vinylbenzyltriphenylphosphonium chloro-codivinylbenzyl alcohol).
[0059] In some embodiments, the polymer is: poly (styrene-sulfonic vinylbenzylalcohol C04-lactic-co-vinylmethylimidazolium bisulfate-codivinylbenzene); poly (styrene-C04 vinylbenzylalcohol-sulfonic-covinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene); poly (styrene-sulfonic vinylbenzyl alcohol C04-lactic-co-vinylbenzylmethylimidazolium bisulfate-codivinylbenzene); poly (styrene-C04 vinylbenzylalcohol-sulfonic-covinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene); or poly (styrene-sulfonic vinylbenzylalcohol C04-lactic-co-vinylbenzyltriphenylphosphonium bisulfate-codivinylbenzene).
[0060] In still other embodiments, the polymer is: poly (butyl-vinylimidazolium bisulfate-co-4-lactic-co-styrene).
[0061] In some embodiments, the polymer described here has one or more catalytic properties selected from: a) disruption of a hydrogen bond in cellulosic materials; b) intercalation of a polymer in crystalline domains of cellulosic materials; and c) cleavage of a glycosidic bond in cellulosic materials.
[0062] In some embodiments, the polymer has greater specificity for cleavage of a glycosidic bond than dehydration of a monosaccharide in cellulosic materials.
[0063] In some embodiments, the polymer is able to degrade the biomass into one or more sugars to a first order velocity constant of at least 0.001 per hour. In other embodiments, the polymer is capable of degrading biomass to produce sugars at a first order velocity constant of at least 0.1, at least 0.15, at least 0.2, at least 0.25, at least minus 0.3 or at least 0.5 per hour.
[0064] In some embodiments, the polymer is capable of converting the biomass into one or more sugars and residual biomass, in which the residual biomass has a degree of polymerization less than 300. In other embodiments, the polymer is capable of converting the biomass in one or more sugars and residual biomass, where the residual biomass has a degree of polymerization of less than 100, less than 90, less than 80, less than 70, less than 60, or less than that 50.
[0065] In some embodiments, the polymer is substantially insoluble in water or an organic solvent.
[0066] A solid particle is also provided which includes a solid core and any of the polymers described herein, wherein the polymer is coated on the surface of the solid core. In some embodiments, the solid core consists of an inert material or a magnetic material. In one embodiment, the solid core is made up of iron.
[0067] In some embodiments, the solid particle is substantially free of pores.
[0068] In other embodiments, the solid particle has catalytic activity. In certain embodiments, at least about 50%, at least 60%, at least 70%, at least 80%, at least 90% of the catalytic activity of the solid particle is present at or near the outer surface of the solid particle.
[0069] A composition is also provided that includes biomass and any of the polymers described herein. In some embodiments, the composition additionally includes a solvent. In one embodiment, the composition further includes water. In some embodiments, the biomass has cellulose, hemicellulose, or a combination thereof. In still other embodiments, biomass also has lignin.
[0070] Also provided is a chemically hydrolyzed biomass composition that includes any of the polymers described herein, one or more sugars and residual biomass. In some embodiments, the one or more sugars and one or more monosaccharides, one or more oligosaccharides, or a mixture thereof. In other embodiments, the one or more sugars are two or more sugars that include at least one C4-C6 monosaccharide and at least one oligosaccharide. In still other embodiments, the one or more sugars are selected from glucose, galactose, fructose, xylose, arabinose and.
[0071] An intermediate saccharification is also provided that includes any of the polymers described here, hydrogen bound biomass. In certain embodiments of intermediate saccharification, the ionic portion of the polymer is the alcohol carbohydrate groups present in cellulose, hemicellulose, and other components that contain hydrogen-bound biomass oxygen. In certain embodiments of intermediate saccharification, the acid portion of the polymer is made up of other components that contain lignocellulosic biomass oxygen, including the glycosidic with the alcohol carbohydrate groups present in the cellulose, hemicellulose-hydrogen bonded, and bonds between the sugar monomers. In some embodiments, the biomass has cellulose, hemicellulose or a combination thereof.
[0072] A method is also provided for the degradation of biomass into one or more sugars, by: a) providing biomass; b) contacting the biomass with any of the polymers described herein and a solvent, for a period of time sufficient to produce a degraded mixture, wherein the degraded mixture has a liquid phase and a solid phase, and the liquid phase comprises one or more sugars , and the solid phase includes residual biomass; c) isolating at least a portion of the liquid phase from the solid phase; and d) recovering one or more sugars from the isolated liquid phase.
[0073] In some embodiments, the isolation of at least a portion of the liquid phase from the solid phase produces a mixture of residual biomass, and the method further includes: i) providing a second biomass; ii) contacting the second biomass with the residual biomass mixture for a period of time sufficient to produce a second degraded mixture, in which the second degraded mixture has a second liquid phase, and a second solid phase, and the second liquid phase includes one or more second sugars, and the second solid phase includes second residual biomass; iii) isolating at least a portion of the second liquid phase from the second solid phase; and iv) recovery of one or more sugars according to the second isolated liquid phase.
[0074] In some embodiments, the method further includes contacting the biomass and the second mixture of residual biomass with a second polymer, wherein the second polymer can be any of the polymers described herein. In other embodiments, the method further includes contacting the biomass and the second mixture of residual biomass with a second solvent. In some embodiments, the method further includes recovering the polymer after isolating at least a portion of the second liquid phase. In certain embodiments of the method, the solvent includes water.
[0075] In some embodiments of the method, the biomass has cellulose and hemicellulose, and the biomass is brought into contact with the polymer and the solvent at a temperature and / or a suitable pressure, preferably to hydrolyze the cellulose or suitable for , preferably, hydrolysis of
[0076] In some embodiments of the method, one or more sugars are selected from one or more monosaccharides, one or more oligosaccharides, or a combination thereof. In certain embodiments, one or more monosaccharides are one or more C4-C6 monosaccharides. In certain embodiments, the one or more sugars are selected from glucose, galactose, fructose, xylose and arabinose.
[0077] In some embodiments, the method also includes pre-treatment of the biomass, before contacting the biomass with the polymer. In certain embodiments, biomass pre-treatment is selected from washing, solvent extraction, swelling-solvent, crushing, grinding, pre-steam treatment, explosive steam pre-treatment, acid pre-treatment is diluted , hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation, wet explosion, ammonia fiber explosion, organosolvent pretreatment, biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical CO2, supercritical HzO, ozone, and gamma irradiation, or a combination of them.
[0078] In some embodiments of the method, the residual biomass has a degree of polymerization less than 300. In other embodiments of the methods, the residual biomass has a degree of polymerization of less than 100, less than 90, less than 80 , less than 70, less than 60 or less than 50.
[0079] In some embodiments of the method, the degradation of biomass to produce sugars that occurs at a first order velocity constant of at least 0.001 per hour. In other embodiments of the method, the degradation of biomass to produce sugars that occurs at a first order velocity constant of at least 0.1, at least 0.15, at least 0.2, at least 0.25, at least minus 0.3 or at least 0.5 per hour.
[0080] A method is also provided for pre-treating biomass before biomass hydrolysis for the production of one or more sugars, by: a) supplying biomass; b) contacting the biomass with any of the polymers described herein and a solvent, for a period of time sufficient to partially degrade the biomass; and c) pre-treatment of the partially degraded biomass before hydrolysis to produce one or more sugars. In some embodiments, the biomass has cellulose, hemicellulose, or a combination thereof. In other embodiments, biomass also has lignin. In some embodiments, the pre-treatment of the partially degraded biomass mixture is selected from washing, solvent extraction, swelling-solvent, crushing, grinding, steam pre-treatment, explosive steam pre-treatment, pre-treatment by acid dilution, hot water pretreatment, alkaline pretreatment, pretreatment lime, wet oxidation, wet burst, ammonia fiber pot burst, organosolvent pretreatment, biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical CO2, supercritical H2O, ozone and gamma radiation or a combination thereof.
[0081] A method of pre-treated biomass hydrolysis is also provided for the production of one or more sugars, by: a) supply of pre-treated biomass according to any of the pre-treatment methods described here; and b) hydrolysis of pre-treated biomass for the production of one or more sugars. In some embodiments, the pre-treated biomass is chemically hydrolyzed or enzymatically hydrolyzed. In some embodiments, the one or more sugars are selected from the group consisting of glucose, galactose, fructose, xylose, and arabinose.
[0082] The use of any of the polymers described herein is also provided for the degradation of biomass into one or more monosaccharides, one or more oligosaccharides, or a combination thereof. In some embodiments, the one or more monosaccharides are one or more C4-C6 monosaccharides. In other embodiments, the one or more sugars are selected from glucose, galactose, fructose, xylose and arabinose. In some embodiments, the biomass has cellulose, hemicellulose, or a combination thereof. In still other embodiments, biomass also has lignin.
[0083] The use of any of the polymers described herein is also provided for the pre-treatment of biomass before further treatment using one or more methods selected from washing, solvent extraction, swelling-solvent, crushing, grinding, pre-treatment steam, explosive steam pretreatment, dilute acid pretreatment, hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation, wet explosion, ammonia fiber explosion, pre -organosolvent treatment, biological pre-treatment, percolation ammonia, ultrasound, electroporation, microwave, supercritical CO2, supercritical H2O, ozone and gamma radiation.
[0084] There is also provided a sugar composition obtained by any of the methods for the degradation of biomass into one or more sugars described herein that employ any of the polymers described herein.
[0085] Also provided is a sugar composition obtained by contacting the biomass with any of the polymers described here, for a period of time sufficient to hydrolyze the biomass in one or more sugars. In some embodiments, the sugar composition that has at least 0.1%, at least 0.2%, at least 0.3%, at least 0.4%, at least 0.5%, at least 0.6 %, at least 0.7%, at least 0.8% or at least 0.9% by weight of a sugar mixture, wherein the sugar mixture comprises one or more C4-C6 monosaccharides and one or more oligosaccharides. In certain embodiments of the sugar composition, the one or more C4-C6 monosaccharides are selected from glucose, galactose, fructose, xylose and arabinose.
[0086] A biofuel composition derived from any of the compositions described herein is also provided. In certain embodiments, the composition includes biofuel, butanol, ethanol, or a mixture thereof.
[0087] A method of preparing any of the polymers described herein is also provided, by: a) providing a starting polymer; b) the reaction of the starting polymer with a compound containing nitrogen, or containing phosphorus to produce an ionic polymer; and c) reacting the ionic polymer with an acid to produce any of the polymers described herein. In some embodiments, the starting polymer is selected from polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, polystyrene, polyurethane, or a combination thereof. In certain embodiments, the starting polymer is a polystyrene. In certain embodiments, the starting polymer is poly (styrene-co-vinylbenzylhalide-co-divinylbenzene). In another embodiment, the starting polymer is poly (styrene-co-vinylbenzylchloro-co-divinylbenzene).
[0088] In some embodiments of the method for preparing any of the polymers described herein, the nitrogen-containing compound is selected from a pyrrolium compound, an imidazolic compound, a pyrazolium compound, an oxazolium compound, a thiazolium compound, a pyridinium compound, a pyrimidinium compound, a pyrazinium compound, a piradizimium compound, a thiazinium compound, a morpholinium compound, a piperidinium compound, a piperizinium compound, and a pyrollizinium compound. In certain embodiments, the nitrogen-containing compound is an imidazolium compound.
[0089] In some embodiments of the method for preparing any of the polymers described herein, the acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and boronic acid. In one embodiment, the acid is sulfuric acid.
[0090] There is also provided a method of preparing any of the polymers described herein, with a polystyrene backbone, by: a) providing a polystyrene; b) reacting the polystyrene with a nitrogen-containing compound to produce an ionic polymer; and c) reacting the ionic polymer with an acid to produce a polymer. In certain embodiments, polystyrene is poly (styrene-co-vinylbenzylhalide-co-divinylbenzene). In one embodiment, polystyrene is poly (styrene-co-vinylbenzylchloro-co-divinylbenzene).
[0091] In some embodiments of the method for preparing any of the polymers described herein having a polystyrene backbone, the nitrogen-containing compound is selected from a pyrrolium compound, an imidazolic compound, a pyrazole compound, an oxazolium compound, a thiazolium, a pyridinium compound, a pyrimidinium compound, a pyrazinium compound, a piradizimium compound, a thiazinium compound, a morpholium compound, a piperidinium compound, a piperizinium compound, and a pyrollizinium compound. In certain embodiments, the nitrogen-containing compound is an imidazolium compound.
[0092] In some embodiments of the method for preparing any of the polymers described herein, having a polystyrene backbone, the acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and boronic acid. In one embodiment, the acid is sulfuric acid.
[0093] A prepared polymer is also provided, according to any of the methods described above. In certain embodiments, the polymer has one or more catalytic properties selected from: a) disruption of a hydrogen bond in cellulosic materials; b) intercalation of a polymer in crystalline domains of cellulosic materials; and c) cleavage of a glycosidic bond in cellulosic materials.
[0094] The use of a prepared polymer according to any of the methods described above for the degradation of biomass into one or more monosaccharides, one or more oligosaccharides, or a combination thereof, is also provided.
[0095] The use of a polymer prepared according to any of the methods described above for partially pre-treated biomass before digestion is also provided, using one or more methods selected from the group consisting of washing, solvent extraction, swelling -solvent, crushing, grinding, steam pretreatment, explosive steam pretreatment, acid dilution pretreatment, hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation , wet blast, ammonia fiber blast, organosolvent pretreatment, biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical CO2, supercritical H2O, ozone and gamma radiation.
[0096] Provided here are polymeric acid catalysts which are polymers that have a plurality of monomers, in which at least one monomer has an acidic unit, and at least one ionic monomer includes a portion (for example, a covalently bonded cationic group that can coordinated to an exchangeable counterion). An exemplary polymer is provided in Formula (I):
where A represents a monomer that has an acidic portion and B represents monomers that have an ionic portion (for example, a cationic unit, a base portion or a salt thereof). The acid portion includes a Bronsted-Lowry acid, and the ionic radical includes a nitrogen-containing functional group. In addition, a and b are stoichiometric coefficients, such that a and b together form a substantial portion of the co-monomer subunits of the polymer. For example, a and b together make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least at least about 90%, at least about 95%, at least about 99% or substantially all of the co-monomer subunits of the polymer.
[0097] In some embodiments, the polymer of Formula 1)) is a polymer of formula (Ia):
which includes C monomers that are covalently bonded to and are cross-linked with other polymer monomers, and c is a stoichiometric coefficient.
[0098] In other embodiments, the polymer of formula (I) is a polymer of general formula (1b):
which includes D monomers that are covalently linked to other monomers in the polymer, and d is a stoichiometric coefficient.
[0099] In other embodiments, the polymer of formula (I) is a polymer of general formula (Ic):

[0100] In certain embodiments, D monomers are non-functionalized moieties, such as hydrophobic moieties (e.g., phenyl).
[0101] Another exemplary polymer is provided in Formula (II):
where each of La and Lb are, independently, for each occurrence of a ligand or absent; each A 'for each occurrence is an acidic portion; each B 'for each occurrence is an ionic radical (for example, cationic); each n is independently, for each occurrence 0, 1, 2, 3, 4, 5, or 6; ea and b are stoichiometric coefficients together, they form a substantial portion of the co-monomer subunits of the polymer. For example, a and b together make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least at least about 90%, at least about 95%, at least about 99% or substantially all of the polymer monomers. Each of the L A 'and L' may independently have a plurality of 'portions and B' A portions, respectively.
[0102] Another exemplary polymer is provided in Formula (III):
where each Ar is, independently, in each occurrence an aryl or heteroaryl group; each A 'for each occurrence is an acidic portion; each B 'for each occurrence is an ionic half (for example, a cationic unit); each XL for each occurrence is a cross-linking portion; and a, b, c, and d are stoichiometric coefficients, such that when taken together they form a substantial portion of the co-monomer subunits of the polymer. For example, a, b, c and c together form at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 99%, or substantially all of the co-monomer subunits of the polymer. Each Ar, independently, can have a plurality of "B portions", "A portions" and "XL portions", respectively.
[0103] Another exemplary polymer is provided in Formula (IV):
where each of Lab is, independently, for each occurrence of a ligand or absent; each AB for each occurrence is a portion comprising an acid and an ionic portion (for example, a cationic unit); each n is independently, for each occurrence 0, 1, 2, 3, 4, 5, or 6; and ab is a stoichiometric coefficient, such that ab becomes a substantial portion of the co-monomer subunits of the polymer. For example, ab becomes at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80% at least about 90%, at least about 95%, at least about 99% or substantially all of the co-monomer subunits of the polymer. Each of the L One independently can have a plurality of acidic parts and ionic moieties (for example, cationic moieties), respectively.
[0104] In the case of polymers, such as Formula (I), (Ia), (Ib), (Ic), (II), (III), or (IV) are represented in this document, connectivity as shown above does not require a polymer block, but can also include other configurations of monomers A and B, including random polymers. In addition, the fixation representation of monomers, such as from A to B, does not limit the nature of the monomer bond, such as A and B via a carbon-carbon bond, but may also include other devices, such as a carbon-heteroatom bond.
[0105] In certain embodiments, the polymer of Formula (I), (la), (lb), (Ic), (II), (III), or (IV) can catalyze the breakdown of polysaccharides, such as cellulose and hemicellulose, for example, by cleaving the glycosidic bond between the sugar moieties. In general, it is the acidic portion on the polymer of Formula (I), (Ia), (Ib), (Ic), (II), (III), or (IV) that catalyzes the dividing of glycosidic bonds. However, the polymer of Formula (I), (Ia), (Ib), (Ic), (II), (III), or (IV) also includes an ionic portion (for example, a cationic unit), which it is usually present as a nitrogen-containing salt. This salt functionality of the polymer of Formula (I), (Ia), (Ib), (Ic), (II), (III), or (IV) can promote the breakdown of the tertiary structure of the polysaccharides described here, as materials cellulosic. For example, the ionic portion can disrupt inter- and intra-molecular hydrogen bonds in the polysaccharide material (for example, by disrupting the tertiary structure of the material), which can allow the acidic portion of the polymer to more easily access the glycosidic bonds of the polysaccharides. Therefore, the combination of the two functional moieties on a single polymer can provide a catalyst that is effective in the decomposition of polysaccharides, using relatively mild conditions, compared to methods that employ a more corrosive acid, or methods that employ severe conditions, such as such as high temperatures or pressure. Brief Description of the Figures
[0106] The following description presents exemplary compositions, methods, parameters and the like. It should be recognized, however, that this description is not intended to be a limitation on the scope of the present disclosure, but rather is provided as a description of exemplary embodiments.
[0107] FIG. 1 illustrates a portion of an exemplary polymer that has a backbone and polymeric side chains.
[0108] FIG. 2 illustrates a part of an exemplary polymer, in which a side chain with the acid group is linked to the polymeric backbone via a linker and in which a side chain with the cationic group is directly linked to the polymeric backbone.
[0109] FIG. 3A illustrates a portion of an exemplificative polymer, in which the monomers are arranged randomly in an alternating sequence.
[0110] FIG. 3B illustrates a portion of an exemplary polymer, in which the monomers are arranged in blocks of monomers, and the block of acidic monomers alternates with the block of ionic monomers.
[0111] Figs. 4A and 4B illustrate a portion of the exemplary crosslinked polymers within a given polymeric chain.
[0112] Figs. 5A, 5B, 5C and 5D illustrate a portion of the exemplary polymers with crosslinking between two polymer chains.
[0113] FIG. 6A illustrates a portion of an exemplary polymer with a polyethylene structure.
[0114] FIG. 6B illustrates a portion of an exemplary polymer with a polyvinyl alcohol backbone.
[0115] FIG. 6C illustrates a portion of an exemplary polymer with an ionomeric backbone.
[0116] FIG. 7A illustrates two side chains in an exemplificative polymer, in which there are three carbon atoms between the side chain with Bronsted-Lowry acid and the side chain with the cationic group.
[0117] FIG. 7B illustrates two side chains in another exemplificative polymer, in which there are zero carbon atoms between the side chain with Bronsted-Lowry acid and the side chain with the cationic group.
[0118] FIG. 8A shows an exemplary arrangement of beta-linear (1-4) -glucan in crystalline cellulose chains.
[0119] FIG. 9 represents the interactions that can occur during saccharification between an exemplificative polymer and the alcohol carbohydrate groups present in the biomass containing crystalline cellulose. Detailed Description of the Invention
[0120] The following description presents exemplary methods, parameters and the like. It should be recognized, however, that this description is not intended to be a limitation on the scope of the present disclosure, but rather is provided as a description of exemplary embodiments.
[0121] Polymers that can be used, in some embodiments, as an acid catalyst to hydrolyze cellulosic materials to produce monosaccharides, as well as oligosaccharides, are described here. Such polymers are referred to herein as "polymeric acid catalysts". In particular, the polymeric acid catalysts provided herein can disturb the hydrogen bonding superstructure, typically found in natural cellulose materials, allowing the acidic pendant groups of the polymer to come into contact with the chemicals of the internal glycosidic bonds in the crystalline areas of cellulose .
[0122] Unlike traditional catalysts known in the state of the art used to hydrolyze cellulosic materials (for example, enzymes, concentrated acids or aqueous diluted acids), the polymeric acid catalysts described herein provide efficient digestion of cellulose, as well as the ease of recycling and reuse. The ability to recycle and reuse the catalyst has several advantages, including reducing the cost of converting lignocellulose into industrially important chemicals, such as sugars, oligosaccharides, organic acids, alcohols and aldehydes. Unlike aqueous diluted enzymes and acids, the polymeric catalysts described here can penetrate deeply into the crystalline structure of cellulose, which results in higher and faster yields for the hydrolysis kinetics of cellulosic materials to produce monosaccharides and / or oligosaccharides. Unlike concentrated acids, which require expensive, energy-intensive solvent extraction and / or distillation processes to recover the acid catalyst following lignocellulose digestion, the polymeric catalysts described here are less corrosive, more easily handled, and it can be easily recovered because they naturally separate from aqueous products. In addition, the use of polymeric acid catalysts provided herein does not require the solubilization of the cellulosic material, in a solvent such as molten metal halides, ionic liquids or organic solvent / acid mixtures. Thus, stable, recyclable polymer catalysts are provided herein that can be effective for digesting cellulosic materials on a commercially viable scale. Definitions
[0123] As used herein, "alkyl" includes monovalent straight-chain or branched-chain saturated hydrocarbon radicals, and combinations thereof, which contain only C and H when unsubstituted. Examples include methyl, ethyl, propyl, butyl and pentyl. When an alkyl residue with a specific number of carbon atoms is called, all geometric isomers with that number of carbon atoms are designed to be involved and described; thus, for example, "butyl", is intended to include w-butyl, sec-butyl, wo-butyl, and that is / t-butyl; "Propyl" includes w-propyl, and wo-propyl. The total number of carbon atoms in each of these groups is sometimes described here. For example, when the group can contain up to ten carbon atoms that can be represented as 1-LOC or as C1-C10 or Cl-10. In some embodiments, alkyl can be substituted. Suitable alkyl substituents can include, for example, hydroxy, amino and halo.
[0124] As used herein, "alkylene" refers to the same residues, as alkyl, but having bivalence. Examples of alkylene include methylene (-CH2-), ethylene (CH2CH2-), propylene (-CH2CH2CH2-), butylene (-CH2CH2CH2CH2-).
[0125] As used herein, "alkylene carbamate" refers to an alkylene radical, in which one or more of the methylene units of the alkylene moiety has been replaced with a carbamate radical (-C (O) -O-NR- or -0-C (O) -NR-, where R can be, for example, alkyl or aryl). In some embodiments, alkylene carbamate can be substituted. Suitable alkylene carbamate substituents may include, for example, hydroxyl, amino and halo.
[0126] As used herein, "alkylene ester" refers to an alkylene radical, in which one or more of the methylene units of the alkylene moiety has been replaced with an ester moiety (-C (O) -O-or - HOLLOW)-). In some embodiments, the alkylene ester can be substituted, still having one or more substituents. Suitable alkylene ester substituents can include, for example, hydroxyl, amino and halo.
[0127] As used herein, "alkylene ester" refers to an alkylene radical, in which one or more of the methylene units of the alkylene moiety has been replaced with an ether moiety (-C (O) -). In some embodiments, alkylene ether can be substituted, still having one or more substituents. Suitable alkylene ether substituents can include, for example, hydroxyl, amino and halo.
[0128] As used herein, "alkenyl" refers to an unsaturated hydrocarbon group having at least one olefinic unsaturation site (i.e., having at least a portion of the formula C = C). Alkenyl contains only C and H when not replaced. When an alkenyl residue having a specific number of carbon atoms is called, all geometric isomers with that number of carbon atoms are designed to be involved and described; thus, for example, "butenyl" is intended to include w-butenyl, sec-butenyl, and wo-butenyl. Examples of alkenyl can include -CH = CH2, - CH2-CH = CH2 and -CH2 ~ CH = CH-CH = CH 2. In some embodiments, alkenyl can be substituted. Suitable alkenyl substituents can include, for example, hydroxy, amino and halo.
[0129] As used herein, "alkenylene" refers to the same residues, as alkenyl, but having bivalence. Examples of alkenylene include ethylene (-CH = CH-), propylene (-CH2CH = CH-) and butylene (-CH2-CH = CH-CH2-).
[0130] As used herein, the term "alkynyl" refers to "an unsaturated hydrocarbon group having at least one acetylenic unsaturation site {that is, having at least a portion of the formula C = C. Alquinyl contains only C and H when unsubstituted When an alkynyl residue having a specific number of carbon atoms is termed, all geometric isomers with that number of carbon atoms are intended to be encompassed described and thus, for example, "pentinyl" is intended to include w - pentynyl, sec-pentynyl, w-pentynyl, i.e. / t-pentynyl. Examples of alkynyl include -C = CH or can -C = C-CH3. In some embodiments, alkynyl may be substituted. Suitable alkynyl substituents may include, for example, hydroxy, amino, and halo.
[0131] As used herein, "aryl" refers to an unsaturated aromatic carbocyclic group having a single ring (eg, phenyl) or multiple condensed rings (eg, naphthyl or anthryl), which condensed rings may or may not be aromatic. Aril contains only C and H when not replaced. An aryl group having more than one ring, where at least one ring is non-aromatic can be attached to the main structure at any position of the aromatic ring or in a non-aromatic ring position. In a variant, an aryl group with more than one ring, where at least one ring is non-aromatic is attached to the main structure at an aromatic ring position. Examples of aryls can include phenyl, phenol and benzyl. In some embodiments, the aryl can be replaced. Suitable aryl substituents can include, for example, alkyl, alkenyl, alkynyl, hydroxy, amino and halo.
[0132] As used herein, "arylene" refers to the same residues, as aryl, but having bivalence.
[0133] As used herein, "cycloalkyl" includes a carbocyclic ring, a non-aromatic group that is bonded through a ring carbon atom, which contains only C and H when unsubstituted. Cycloalkyl may consist of a ring, such as cyclohexyl, or multiple rings, such as adamantyl. A cycloalkyl with more than one ring can be fused, spiro or bridged, or combinations thereof. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and decahydronefitalenyl. In some embodiments, cycloalkyl may be substituted. Suitable cycloalkyl substituents can include, for example, alkyl, hydroxy, amino and halo.
[0134] As used herein, "cycloalkylene" refers to the same residues, as cycloalkyl, but having bivalence.
[0135] As used herein, "heteroaryl" refers to an unsaturated aromatic carbocyclic group having 1 to 10 ring carbon atoms and at least one ring heteroatom, including but not limited to hetero atoms, such as nitrogen , oxygen and sulfur. A heteroaryl group may have a single ring (eg, pyridyl, pyridinyl, imidazolyl) or multiple condensed rings (eg, indolizinyl, benzothienyl) that have condensed rings may or may not be aromatic. A heteroaryl group having more than one ring, where at least one ring is non-aromatic can be attached to the main structure at any position of the aromatic ring or in a non-aromatic ring position. In a variant, a heteroaryl group having more than one ring, where at least one ring is non-aromatic is attached to the main structure at one position of the aromatic ring. Examples of heteroaryls can include pyridyl, pyridinyl, imidazolyl, thiazolyl and. In some embodiments, heteroaryl can be substituted. Suitable heteroaryl substituents can include, for example, alkyl, alkenyl, alkynyl, hydroxy, amino and halo.
[0136] As used herein, "heteroarylene" refers to the same residues, as heteroaryl, but having bivalence.
[0137] It should be understood that the alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, ether, ester, carbamate can be substituted, where the group or groups, in particular, to be described may not have any substituents other than hydrogen , or the group or groups may have one or more substituents other than hydrogen. If not specified otherwise, the total number of such substituents that may be present is equal to the number of H atoms present in the form unsubstituted with the group to be described. Polymeric Acid Catalysts
[0138] In one aspect, the acidic polymer catalysts provided herein are polymers consisting of acidic monomers and ionic monomers (which are also known as "ionomers), bonded to form a polymeric structure. Each acidic monomer includes at least one acid Bronsted-Lowry, and each ionic monomer includes at least one nitrogen-containing cationic group or a phosphorus-containing cationic group. Some of the acidic and ionic monomers may also include a linker that binds the cationic group is Bronsted-Lowry acid, respectively, polymeric structure. For acidic monomers, Bronsted-Lowry acid and the ligand together form a side chain. Similarly, for ionic monomers, the cationic group and the ligand together form a side chain. to the portion of the exemplary polymer shown in Figure 1, the side chains are pendent from the polymeric main chain. a) Acid and ionic monomers
[0139] The polymers described herein contain monomers that have at least one Bronsted-Lowry acid and at least one cationic group. Bronsted-Lowry acid and the cationic group can be of different monomers or on the same monomer.
[0140] In some embodiments, the acid monomers may have a Bronsted-Lowry acid. In other embodiments, the acid monomers can have two or more Bronsted-Lowry acids, as is chemically viable. When acidic monomers have two or more Bronsted-Lowry acids, the acids can be the same or different.
[0141] Suitable Bronsted-Lowry acids can include any Bronsted-Lowry acid that can form a covalent bond with a carbon atom. Bronsted-Lowry acids can have a pK value of less than about 7, less than about 6, less than about 5, less than about 4, less than about 3, less than about 2, less than about 1, or less than zero. In some embodiments, Bronsted-Lowry acid at each occurrence can be independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluoric acid.
[0142] The acidic monomers of the polymer may either all have the same as Bronsted-Lowry acid, or they may have different Bronsted-Lowry acids. In an exemplificative embodiment, each Bronsted-Lowry acid, in which the polymer is sulfonic acid. In another exemplary embodiment, each of the Bronsted-Lowry acids, where the polymer is phosphonic acid. In yet another exemplary embodiment, Bronsted-Lowry acid, in some monomers of which the polymer is sulfonic acid, while Bronsted-Lowry acid in other monomers of which the polymer is phosphonic acid.
[0143] In some embodiments, ionic monomers may have a cationic group. In other embodiments, ionic monomers can have two or more cationic groups, as is chemically feasible. When ionic monomers have two or more cationic groups, the cationic groups can be the same or different.
[0144] Suitable cationic groups can include any nitrogen-containing cationic group or a phosphorus-containing cationic group. In some embodiments, the nitrogen-containing cationic group, in each occurrence, independently, can be selected from ammonium, pyrrole, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, piradizimio, tiazinio, morfolinio, piperidinio, piperizinio, and pyrolysis. In other embodiments, the cationic group containing phosphorus, in each occurrence, independently, can be selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichlor phosphonium, and trifluoro phosphonium.
[0145] Ionic monomers can either all have the same cationic group, or they can have different cationic groups. In some embodiments, each cationic group in the cationic polymer is a nitrogen-containing group. In other embodiments, each cationic group in the cationic polymer is a group containing phosphorus. In still other embodiments, the cationic group in some monomers of which the cationic polymer is a group containing nitrogen, while the cationic group in other monomers of which the cationic polymer is a group containing phosphorus. In an exemplary embodiment, each cationic group in the polymer is imidazolium. In another exemplary embodiment, the cationic group in some monomers of which the polymer is imidazolium, while the cationic group in other monomers of the polymer is pyridinium. In yet another exemplary embodiment, each cationic group in which the polymer is a substituted phosphonium. In yet another exemplary embodiment, the cationic group in some monomers of which the polymer is triphenyl phosphonium, while the cationic group in other monomers of the polymer is imidazolium.
[0146] In some embodiments, the cationic group can coordinate with a counterion. For example, the counterion can be a halide (for example, bromide, chloride, iodide, and fluorine), nitrate (NO3 *), sulfate (SO42-), formate (HCOO), acetate (HsCOO-), or an organosulfanate (R -SO3-; where R is an organic functional group, for example, methyl, phenyl).
[0147] In other embodiments, the cationic group can coordinate with a Bronsted-Lowry acid in the polymer. At least a portion of the Bronsted-Lowry acids and the cationic groups of the polymer can form inter-monomeric ionic associations. Inter-monomeric ionic associations result in the formation of salts between the monomers in the polymer, rather than with external counterions. In some exemplary embodiments, the proportion of acid monomers involved in ionic inter-monomer associations to the total number of acid monomers can be a maximum of 90% internally-coordinated, a maximum of 80% internally-coordinated, a maximum of 70% internally-coordinated, maximum 60% internally-coordinated, maximum 50% internally-coordinated, maximum 40% internally-coordinated, maximum 30% internally-coordinated, maximum 20% internally-coordinated, maximum , 10% internally-coordinated, maximum 5% internally-coordinated, maximum 1% internally-coordinated, or less than 1% internally-coordinated. It must be understood that internally coordinated sites are less likely to ion exchange with a solution that is brought into contact with the polymer.
[0148] Some of the monomers in the polymer contain both Bronsted-Lowry acid and the cationic group in the same monomer. Such monomers are referred to as "acid-ionic" monomers. In exemplary embodiments, a side chain of an acid-ionic monomer may contain imidazole and acetic acid, or boronic acid and pyridinium.
[0149] With reference to the portion of an exemplary polymer shown in FIG. 2, Bronsted-Lowry acid and the cationic group in the side chains of the monomers can be directly linked to the polymeric structure or linked to the polymeric backbone, through a ligand.
[0150] Suitable binders may include, for example, substituted or unsubstituted alkylene, unsubstituted or substituted cycloalkylene, substituted or unsubstituted alkenylene, unsubstituted or substituted arylene, substituted or unsubstituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester and unsubstituted or substituted alkylene carbamate. In some embodiments, the binder is an unsubstituted or substituted C5 or C6 arylene. In certain embodiments, the binder is unsubstituted or substituted phenylene. In an exemplary embodiment, the binder is unsubstituted phenylene. In another exemplary embodiment, the linker is substituted phenylene (for example, substituted hydroxy-phenylene).
[0151] Furthermore, it should be understood that some or all of the acidic monomers linked to the polymeric backbone via a linker can have the same linker, or have, independently, different linkers. Likewise, some or all of the ionic monomers linked to the polymeric backbone through a linker can have the same linker, or have, independently, different linkers. In addition, some or all of the acidic monomers linked to the polymeric backbone via a linker may have the same or different ligands as some or all of the ionic monomers linked to the polymeric backbone via a linker.
[0152] In certain embodiments, the acid monomers may have a side chain with a Lowry-Bronsted acid that is linked to the polymeric backbone via a linker. Side chains with one or more Bronsted-Lowry acids linked by a linker may include, for example,
As used herein, - / VVVVk indicates the point of attachment to the polymeric backbone.
[0153] In other embodiments, the acid monomers may have a side chain with a Bronsted-Lowry acid, which is directly linked to the polymeric backbone. Side chains with a Bronsted-Lowry acid directly attached to the polymer backbone can include, for example,

[0154] In certain embodiments, ionic monomers may have a side chain with a cationic group, which is linked to the polymeric backbone via a linker. Side chains with one or more cationic groups linked by a linker can include, for example,





[0155] In other embodiments, ionic monomers may have a side chain with a cationic group, which is directly linked to the polymeric backbone. Side chains with a nitrogen-containing cationic group directly attached to the polymeric structure may include, for example,

[0156] Side chains with a cationic group containing phosphorus directly attached to the polymeric skeleton may include, for example,

[0157] In other embodiments, monomers may have a side chain that contains both a Bronsted-Lowry acid and a cationic group, in which the Bronsted-Lowry acid is attached to the polymeric backbone, via a linker or the cationic group it is connected to the polymeric skeleton through a ligand. Monomers that have side chains that contain both a Bronsted-Lowry acid and a cationic group, can also be called acidic "ionomers". Such side chains of ionic acid monomers that are linked by a linker may include, for example,

[0158] In other embodiments, monomers may have a side chain that contains both a Bronsted-Lowry acid and a cationic group, where Bronsted-Lowry acid is directly linked to the polymeric backbone, the cationic group is directly linked to the skeleton polymeric, or both Bronsted-Lowry acid and the cationic group are directly linked to the polymeric chain. Such side chains of ionic acid monomers may include, for example,

[0159] In some embodiments, ionic monomers and acids form a substantial part of the polymer. In certain embodiments, acidic and ionic monomers become at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the polymer monomers, based on the ratio of the number of monomers in the polymer.
[0160] The ratio of the total number of acidic monomers to the total number of ionic monomers can be varied to adjust the strength of the acid catalyst. In some embodiments, the total number of acidic monomers exceeds the total number of ionic monomers in the polymer. In other embodiments, the total number of acidic monomers is at least 2, at least 3, at least 4, at least 5, at least 7, at least 8, at least 9, or at least 10 times the total number of ionic monomers in the polymer. In certain embodiments, the ratio of the total number of acidic monomers to the total number of ionic monomers is 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.
[0161] In some embodiments, the total number of ionic monomers exceeds the total number of acidic monomers in the polymer. In other embodiments, the total number of ionic monomers is at least 2, at least 3, at least 4, at least 5, at least 7, at least 8, at least 9, or at least 10 times the total number of acidic polymer monomers. In certain embodiments, the ratio of the total number of ionic monomers to the total number of acidic monomers is 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.
[0162] The polymers described here can be characterized by the chemical functionalization of the polymer. In some embodiments, the polymer can be between 0.1 and 20 mmol, between 0.1 and 15 mmol, between 0.01 and 12 mmol, between 0.01 and 10 mmol, between 1 and 8 mmol, between 2 and 7 mmol, between 3 and 6 mmol, between 1 and 5, or between 3 and 5 mmol of Bronsted-Lowry acid per gram of polymer. In particular embodiments, where the polymer has at least some monomers with sulfonic acid side chains such as Bronsted-Lowry acid, the polymer can have between 0.05 and 10 mmol of sulfonic acid per gram of the polymer. In other embodiments where the polymer has at least some monomers with phosphoric acid side chains such as Bronsted-Lowry acid, the polymer may have between 0.01 and 12 mmol of phosphonic acid per gram of the polymer. In other embodiments where the polymer has at least some monomers with side chains with acetic acid such as Bronsted-Lowry acid, the polymer can have between 0.01 and 12 mmol of acetic acid per gram of polymer. In other embodiments in which the polymer has at least a few monomers with isophthalic acid side chains such as Bronsted-Lowry acid, the polymer may have between 0.01 and 5 mmol of isophthalic acid per gram of the polymer. In other embodiments where the polymer has at least some Bronsted-Lowry acid, the polymer can have between 0.01 and 20 mmol of boronic acid per gram of the polymer. In other embodiments in which the polymer has at least some with perfluorinated monomers having acid side chains such as Bronsted-Lowry acid, the polymer can have between 0.01 and 5 mmol of the perfluoric acid per gram of the polymer.
[0163] In some embodiments, the polymer can be between 0.01 and 10 mmol, between 0.01 and 8.0 mmol, between 0.01 and 4 mmol, between 1 and 10 mmol, between 2 and 8 mmol, or between 3 and 6 mmol of ionic group. In such embodiments, the ionic group includes the cationic group listed, as well as any suitable counterions described herein (for example, halide, nitrate, sulfate, formate, acetate, or organo-sulfonate). In particular embodiments where the polymer has at least some monomers with side chains having imidazolium as part of the ionic group, the polymer can have between 0.01 and 8 mmol of the ionic group per gram of the polymer. In other embodiments in which the polymer has at least some side chain monomers having pyridinium as part of the ionic group, the polymer can have between 0.01 and 8 mmol of the ionic group per gram of the polymer. In other embodiments, where the polymer has at least some side chain monomers having triphenyl phosphonium, as part of the ionic group, the polymer can have between 0.01 and 4 mmoles of the ionic group per gram of the polymer. b) Hydrophobic monomers
[0164] The polymers described herein may further include monomers having a side chain containing a non-functional group, such as a hydrophobic group. In some embodiments, the hydrophobic group is attached directly to the polymeric backbone. Suitable hydrophobic groups can include, for example, unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl. In some embodiments, the hydrophobic group is substituted or unsubstituted C5 or C6 aryl. In certain embodiments, the hydrophobic group is unsubstituted or substituted phenyl. In an exemplary embodiment, the hydrophobic group is unsubstituted phenyl. In addition, it should be understood that the hydrophobic monomers can either all have the same hydrophobic group, or can have different hydrophobic groups. c) Alignment of monomers
[0165] In some embodiments, acidic monomers, ionic monomers, ionic acid monomers and hydrophobic monomers, when present, can be arranged in alternating sequence or in random order as monomer blocks. In some embodiments, each block has no more than twenty, fifteen, ten, six or three monomers.
[0166] In some embodiments, the polymer is arranged randomly in an alternating sequence. With reference to the exemplary polymer portion shown in FIG. 3A, the monomers are randomly arranged in an alternating sequence.
[0167] In other embodiments, the polymer is arranged randomly in blocks of monomers. With reference to the exemplary polymer portion shown in FIG. 3B, the monomers are arranged in blocks of monomers.
[0168] The polymers described herein can also be cross-linked. Such crosslinked polymers can be prepared by introducing crosslinking groups. In some embodiments, crosslinking can occur within a given polymeric chain, with reference to the portion of the exemplary polymers shown in Figs. 4A and 4B. In other embodiments, crosslinking can occur between two or more polymer chains, with reference to the exemplary polymer portion in FIGS. 5A, 5B, 5C and 5D.
[0169] With reference to fig. 4A, 4B and 5A, it should be understood that R1, R2 and R3, respectively, are exemplary crosslinking groups. Suitable crosslinking groups that can be used to form a polymer crosslinked with the polymers described herein include, for example, substituted or unsubstituted divinyl alkanes, substituted or unsubstituted divinyl cycloalkanes, substituted or unsubstituted divinyl aryl, substituted or unsubstituted heteroaryls substituted, dihaloalkanes, dihaloalkenes, dihaloalkans. For example, crosslinking groups can include divinylbenzene, diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane, divinylethane, dichloroethane, divinylpropane, dichloropropane, divinylbutane, dichlorobutane, ethylene glycol and resorcinol. d) Polymeric structure
[0170] The polymeric structure described herein can include, for example, polyalkylenes, polyalkenyl alcohols, polycarbonate, polyarylenes, polyarylethylketones, and polyamide-imides. In certain embodiments, the polymeric structure can be selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly (acrylonitrile-butadiene-styrene).
[0171] With reference to FIG. 6A, in an exemplary embodiment, the polymeric backbone is polyethylene. With reference to FIG. 6B, in another exemplary embodiment, the polymeric structure is polyvinyl alcohol.
[0172] The polymeric structure described here may also include an integrated ionic group as part of the polymeric backbone. Such polymeric skeletons can also be called "ionomeric skeletons". In certain embodiments, the polymeric structure may be selected from polialquilenoamônio, polialquilenodiamônio, polialquilenopirrolio, polialquilenoimidazolio, polialquilenopirazolio, polialquilenooxazolio, polialquilenotiazolio, polialquilenopiridinio, polialquilenopirimidinio, polialquilenopirazinio, polialquilenopiradizimio, polialquilenotiazinio, polialquilenomorfolinio, polialquilenopiperidinio, polialquilenopiperizini, polialquilenopirolizinio, polialquilenotrifenilfosfônio, polialquilenotrimetilfosfônio, polialquilenotrietilfosfônio , polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium, polyalkylenetrichlorophosphonium, polyalkylenetrifluorophosphonium, and polyalkylenediazole.
[0173] With reference to FIG. 6C, in yet another exemplary embodiment, the polymeric structure is a polyalkyleneimidazole.
[0174] In addition, the number of atoms between side chains in the polymer backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, or zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone. With reference to FIG. 7A, in an exemplary embodiment, there are three carbon atoms between the side chain with Bronsted-Lowry acid and the side chain with the cationic group. In another example, with reference to FIG. 7B, there is zero between the atoms in the side chain with the acidic portion and the side chain with the ionic portion.
[0175] It should be understood that polymers can include any of the Bronsted-Lowry acids, cationic groups, counterions, ligands, hydrophobic groups, cross-linked groups, and polymeric skeletons described herein, as if each and every all combinations were listed separately. For example, in one embodiment, the polymer may include benzenesulfonic acid (i.e., a sulfonic acid with a phenyl linker) attached to a polystyrene backbone, and an imidazolium chloride attached directly to the polystyrene backbone. In another embodiment, the polymer can include bornyl-benzyl-pyridinium chloride (i.e., a boronic acid and pyridinium chloride from the same monomer unit with a phenyl linker) attached to a polystyrene backbone. In yet another embodiment, the polymer can include benzenesulfonic acid and a portion of imidazolium sulfate each individually attached to a polyvinyl alcohol backbone.
[0176] Examples of polymers described herein include: poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazol-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-nitrate-co-poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- ( 4-vinylbenzyl) -3H-imidazole-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-iodide-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-bromide-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-formate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-chloride-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-bromide-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-iodide-co-3-methyl-l- (4-vinylbenzyl) - 3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-bisulfate-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1- (4-vinylbenzyl) -pyridine-acetate-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-formate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triphenyl- (4-vinylbenzyl) -phosphono chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triphenyl- (4-vinylbenzyl) -phosphono bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic -co-triphenyl- (4-vinylbenzyl) -phosphono acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1-methyl-1- (4-vinylbenzyl) -pipererdin-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1-methyl-1- (4-vinylbenzyl) -pipererdin-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-1-methyl-1- (4-vinylbenzyl) -pipererdin-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4- (4-vinylbenzyl) -morpholinae-4-oxide-co-divinyl benzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium acetate-co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazol-1-chloride-co-4-boronyl-1- (4-vinylbenzyl) -pyridine chloride-co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-1- (4-vinylphenyl) methylphosphonic acid -co- divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-1- (4-vinylphenyl) methylphosphonic acid -co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-1- (4-vinylphenyl) methylphosphonic acid -co- divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4- (4-vinylbenzyl) -morpholinee-4-oxide-co-divinyl benzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) -isophthalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) -isophthalic acid -co-3-methyl-1- (4-vinylbenzyl) -3 / 7-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) - isofithalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co- 3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co- 3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co- 3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole chloride-co-vinylbenzylmethylmorpholine divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole chloride-co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenyl phosphone chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole bisulfate-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole bisulfate-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole acetate-co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenyl phosphone acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole acetate-co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenyl phosphone acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene) poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole chloride-co-divinyl); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole nitrate-co-divinylbenzene); vinylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole acetate-co-divinylbenzene); vinylbenzylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (butyl-vinylimidazole chloride-co-butylimidazole bisulfate-co-4-vinylbenzenesulfonic acid); poly (butyl vinylimidazole bisulfate-co-butylimidazole bisulfate-co-4-vinylbenzenesulfonic acid); poly (benzyl acid alcohol-co-4-vinylbenzyl alcohol sulfonic -co-vinylbenzyltriphenylphosphono chloride-co- poly (benzyl acid alcohol-co-4-vinylbenzyl alcohol sulfonic -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzyl alcohol). Properties of polymeric acid catalysts
[0177] The polymers described herein have one or more catalytic properties. As used herein, a "catalytic property" of a material is a physical and / or chemical property that increases the rate and / or extent of a reaction that involves the material. The catalytic properties can include at least one of the following properties: a) a rupture of a hydrogen bond in cellulosic materials; b) intercalation of a polymeric acid catalyst in crystalline domains of cellulosic materials; and c) cleavage of a glycosidic bond in cellulosic materials. In other embodiments, polymeric acid catalysts have two or more of the catalytic properties described above, or all three of the catalytic properties described above.
[0178] In certain embodiments, the polymeric acid catalysts described here have the ability to catalyze a chemical reaction by donating a proton, and can be regenerated during the reaction process.
[0179] In some embodiments, the polymers described herein have greater specificity for cleavage of a glycosidic bond than dehydration of a monosaccharide. Solid particles
[0180] The polymers described here can form solid particles. A person skilled in the art recognizes the various techniques and methods known for making solid particles. For example, a solid particle can be formed through emulsion or dispersion polymerization procedures, which are known to a person skilled in the art. In other embodiments, solid particles can be formed by grinding or breaking the polymer into particles, which are also techniques and methods that are known to a person skilled in the art.
[0181] In certain embodiments, the solid particles are substantially free of pores. In certain embodiments, where solid particles are substantially free from pores, solid particles contain no more than 50%, no more than 40%, no more than 30%, no more than 20%, at most, 15 %, no more than 10%, no more than 5%, or no more than 1% pores. Such particles can be advantageously provided that soluble species and solvents (for example, sugars) are less likely to permeate in the solid particle.
[0182] In other embodiments, the solid particles include a microporous gel resin. In still other embodiments, the solid particles include a macroporous gel resin.
[0183] Other methods known in the art for preparing solid particles include the coating polymers described herein on the surface of a solid core. The solid core can be a non-catalytic support. Suitable materials for the solid core may include an inert material (for example, aluminum oxide, corn cob, ground glass, plastic chips, pumice, silicon carbide, or nutshell) or a magnetic material. Polymer-coated core particles can be made using techniques and methods that are known to a person skilled in the art, for example, by dispersion polymerization of growing a cross-linked polymer shell around the core material, or by coating by spraying or melting.
[0184] The solid particles coated with the polymer described herein have one or more catalytic properties. In some embodiments, at least about 50%, at least 60%, at least 70%, at least 80% or at least 90% of the catalytic activity of the solid particle is present on or near the outer surface of the solid particle.
[0185] This form of polymeric acid catalysts can be advantageous over other catalysts known in the art due to, for example, ease of handling. The nature of solid polymeric catalysts may be due to the ease of recycling (for example, by filtration of the catalyst), without the need for distillation or extraction methods. For example, the particle density and size can be selected in such a way that the catalyst particles can be separated from the materials used in a process for the distribution of biomaterials. Particles can be selected based on the sedimentation rate, for example, in relation to the materials used or produced in a reaction mixture, the particle density, or the particle size. Alternatively, solid particles coated with polymeric acid catalysts having a magnetically active core can be recovered by electromagnetic methods known to a person skilled in the art. Saccharification using polymeric acid catalysts
[0186] In one aspect, methods for saccharification of cellulosic materials (e.g., biomass) using the polymeric acid catalysts described herein are provided. Saccharification refers to the hydrolysis of cellulosic materials (for example, biomass) into one or more sugars, by breaking down the complex carbohydrates of cellulose (and hemicellulose, if any) in the biomass. The one or more sugars can be monosaccharides and / or oligosaccharides. As used herein, "Oligosaccharide" refers to a compound that contains two or more units of monosaccharides linked by glycosidic bonds. In certain embodiments, the one or more sugars are selected from glucose, cellobiose, xylose, xylulose, arabinose, mannose and galactose.
[0187] It should be understood that cellulosic material can be subjected to one stage of a hydrolysis process or a multi-stage. For example, in some embodiments, the cellulosic material is first contacted with the polymeric acid catalyst, and then the resulting product is brought into contact with one or more enzymes in a second hydrolysis reaction (for example, using enzymes).
[0188] The one or more sugars obtained from the hydrolysis of cellulosic material can be used in a fermentation process for the subsequent production of biofuels (for example, ethanol) and other bio-based chemicals. For example, in some embodiments, the one or more sugars obtained by the methods described herein can be subjected to subsequent bacterial or yeast fermentation for the production of biofuels and other bio-based chemicals.
[0189] Furthermore, it should be understood that any method known in the prior art, which includes pre-treatment, enzymatic hydrolysis (saccharification), fermentation, or a combination thereof, can be used with polymeric acid catalysts in methods described here. Polymeric acid catalysts can be used before or after pre-treatment methods to make cellulose (hemicellulose, where present) in biomass more accessible to hydrolysis. a) Cellulosic materials
[0190] Cellulosic materials can include any material that contains cellulose and / or hemicellulose. In certain embodiments, cellulosic materials can be lignocellulosic materials that contain lignin, in addition to cellulose and / or hemicellulose. Cellulose is a polysaccharide that includes a linear chain of beta- (1-4) -D-glucose units. Hemicellulose is also a polysaccharide; however, unlike cellulose, hemicellulose is a branched polymer that typically includes short chains of sugar units. Hemicellulose may include a diverse number of sugar monomers, including, for example, xylans, xyloglucans, arabinoxylans and mannans.
[0191] Cellulosic materials can usually be found in biomass. In some embodiments, the biomass used with the polymeric acid catalysts sold described herein contains a substantial proportion of cellulosic material, such as 5%, 10%, 15%, 20%, 25%, 50%, 75%, 90% or greater than 90% cellulose. In some embodiments, cellulosic materials may include herbaceous materials, agricultural residues, forest residues, solid urban residues, paper residues and cellulose and paper residues. In certain embodiments, the cellulosic material is corn straw, corn fiber or corn cob. In other embodiments, the cellulosic material is bagasse, rice straw, wheat straw, switchgrass or miscellaneous. In still other embodiments, the cellulosic material may also include chemical cellulose (for example, Avicel), industrial cellulose (for example, paper or pulp), bacterial, algae or cellulose. As described herein and known in the art, cellulosic materials can be used as obtained from the source, or can be subjected to one or pre-treatments. For example, pretreated corn straw ("PCS") is a cellulosic material derived from corn straw by heat treatment and / or diluted sulfuric acid, and is suitable for use with the polymeric acid catalysts described herein.
[0192] Several different crystalline structures of cellulose are known in the art. For example, with reference to FIG. 8, crystalline cellulose are forms of cellulose, where beta-linear (1-4) -glucan chains can be packaged in a three-dimensional superstructure. The aggregated beta (1-4) -glucan chains are normally held together via inter- and intra-molecular hydrogen bonds. The steric impediment that results from the structure of crystalline cellulose may prevent the access of reactive species, such as enzymes or chemical catalysts, to the beta-glycosidic bonds in the glucan chains. In contrast, non-crystalline cellulose and amorphous cellulose are forms of cellulose in which beta- (1-4) -glucan individual chains are not appreciably packaged in a hydrogen-bound superstructure, where access by beta-reactive species glycoside linked to cellulose is hampered.
[0193] A person skilled in the art will recognize that natural sources of cellulose may include a mixture of crystalline and non-crystalline domains. The regions of a beta- (1-4) -glucan chain, where the sugar units are present in their crystalline form are referred to herein as the "crystalline domains" of the cellulosic material. Generally, the beta- (1-4) -glucan chain present in natural cellulose exhibits an average degree of polymerization between 1,000 and 4,000 anhydroglucose ("AHG") units (ie, 1,000-4,000 glucose molecules linked through bonds) beta-glycosidic), while the number of average degree of polymerization for the crystalline domains is typically between 200 and 300 AHG units. See, for example, R. Rinaldi, R. Palkovits, and F. Schiith, Angew. Chem. Int. Ed, 47, 8047 - 8050 (2008); Y.-HP Zhang and LR Lynd, Biomacromolecules, 6, 1501-1515 (2005).
[0194] Typically, cellulose has several crystalline domains that are connected by non-crystalline binders that can include a small number of anhydrous units. A person skilled in the art will recognize that traditional methods for digesting biomass, such as dilute acid conditions, can digest the non-crystalline domains of natural cellulose, but not the crystalline domains. The acid treatment is diluted not to significantly disturb the packaging of individual beta- (1-4) -glucan chains in a hydrogen-bound superstructure, nor to hydrolyze an appreciable number of glycosidic bonds in beta-packed to (1-4) chains -glucan. Therefore, the treatment of cellulosic materials with natural diluted acid reduces the number of average degree of polymerization of incoming cellulose to about 200-300 units of anhydroglucose, but does not further reduce the degree of polymerization of cellulose to below 150- 200 units of anhydroglucose (which is the typical size of
[0195] In certain embodiments, the polymeric acid catalysts described herein can be used to digest natural cellulosic materials. The polymeric acid catalysts can be used to digest crystalline cellulose by a chemical transformation in which the average degree of polymerization of the cellulose is reduced to a value lower than the average degree of polymerization of the crystalline domains. The digestion of crystalline cellulose can be detected by observing a reduction in the average degree of cellulose polymerization. In certain embodiments, polymeric acid catalysts can reduce the average degree of polymerization of cellulose from at least 300 AGH units to less than 200 AHG units.
[0196] It should be understood that the polymeric acid catalysts described herein can be used to digest crystalline cellulose, as well as microcrystalline cellulose. A person skilled in the art will recognize that crystalline cellulose typically has a mixture of crystalline and amorphous or non-crystalline domains, whereas microcrystalline cellulose typically refers to a form of cellulose in which amorphous or non-crystalline domains were removed by chemical treatment such that the residual cellulose has substantially only crystalline domains. b) Pre-treatment of cellulosic materials
[0197] In some embodiments, the polymeric acid catalysts described herein can be used with cellulosic materials that have been pretreated. In other embodiments, the polymeric acid catalysts described herein can be used with cellulosic materials, before pretreatment.
[0198] Any pretreatment process known in the art can be used to destroy components of the plant cell wall of cellulosic material, including, for example, chemical or physical pretreatment processes. See, for example, Chandra et ah, Pre-treatment substrate: The key to effective enzymatic hydrolysis of lignocellulose , Adv. Biochem. Engin / Biotechnol., 108 :. 67-93 (2007); Galbe and Zacchi, pretreatment of lignocellulosic materials for the production of efficient bioethanol, Adv. Biochem. Engin / Biotechnol., 108 :. 41-65 (2007); Hendriks and Zeeman, pre-treatments to improve the digestibility of lignocellulosic biomass, Bioresource Technol., 100: 10-18 (2009); Mosier et al, Characteristics of promising technologies for the pre-treatment of lignocellulosic biomass, Bioresource Technol, 96: 673-686 (2005); Taherzadeh and Karimi, Pre-treatment of lignocellulosic residues to improve the production of ethanol and biogas: A review, Int. J. ofMol. Sci., 9: 1621-1651 (2008); Yang and Wyman, pretreatment: the key to unraveling low-cost cellulosic ethanol, biofuels and bioproducts Bio refining (Biofpr), 2: 26-40 (2008). Examples of appropriate pre-treatment methods are described by Schell et al. (Appl Biochem Biotechnol e, 105-108: 69-85 (2003) and Mosier et al (Bioresource Technol, 96: 673-686 (2005), and in US Patent Application No. 2002/0164730.
[0199] In other embodiments, the polymeric acid catalysts described herein can be used with cellulosic materials that have not been previously treated. In addition, the cellulosic material can also be subjected to other processes, instead of or in addition to the pre-treatment, including, for example, particle size reduction, pre-immersion, wetting, cleaning or conditioning.
[0200] Furthermore, the use of the term "pre-treatment" does not imply or require any specific moment in the steps of the methods described here. For example, cellulosic material can be pre-treated before hydrolysis. Alternatively, pretreatment can be carried out simultaneously with hydrolysis. In some embodiments, the pre-treatment step itself results in some conversion of biomass to sugars (for example, even in the absence of the polymeric acid catalysts described here).
[0201] Several common methods that can be used for pretreating cellulose materials for use with polymeric acid catalysts are described below. Steam pretreatment
[0202] the cellulosic material is heated to disrupt the components of the cell walls of the plant (for example, lignin, hemicellulose, cellulose) to make cellulose and / or hemicellulose more accessible to enzymes. Cellulosic material is typically passed to or through a reaction vessel, where the steam is injected to raise the temperature to the desired temperature and the pressure is retained within it for the desired reaction time.
[0203] In certain embodiments in which steam pretreatment is used to pretreat cellulosic materials, pretreatment can be carried out at a temperature between 140 ° C and 230 0 C, between 160 0 C and 200 ° C, or between 170 ° C and 190 ° C. It should be understood, however, that the ideal temperature range for steam pretreatment may vary depending on the polymeric acid catalyst used.
[0204] In certain embodiments, the residence time for steam pretreatment is 1 to 15 minutes, 3 to 12 minutes, or 4 to 10 minutes. It should be understood, however, that the ideal residence time for steam pretreatment can vary depending on the temperature range and the polymeric acid catalyst used.
[0205] In some embodiments, the steam pretreatment can be combined with an explosive discharge of the material after the pretreatment, which is known as steam subject to explosions a rapid blinking at atmospheric pressure and a turbulent flow of the material to increase the surface area accessible by fragmentation. See Duff and Murray, Bioresource Technol, 855: 1-33 (1996); Galbe and Zacchi, Appl. Microbiol. Biotechnol., 59: 618-628 (2002); US Patent Application No. 2002/0164730.
[0206] During steam pretreatment, acetyl groups in hemicellulose can be cleaved, and the resulting acid can autocatalyze partial hydrolysis of hemicellulose into monosaccharides and / or oligosaccharides. A person skilled in the art will recognize, however, that lignin (when present in cellulosic material) is removed only to a limited extent. Thus, in certain embodiments, a catalyst such as sulfuric acid (typically 0.3% to 3% w / w) can be added prior to steam pretreatment, to decrease time and temperature, increase recovery, and improve enzymatic hydrolysis. See Ballesteros et ah, Appl. Biochem. Biotechnol, 129-132: 496-508 (2006); Varga et al, Appl. Biochem. Biotechnol, 113-116: 509-523 (2004); Sassner et al, Enzyme Microb. Technol, 39: 756-762 (2006). Chemical pretreatment
[0207] Chemical pretreatment of cellulosic materials, can promote the separation and / or release of cellulose, hemicellulose, and / or lignin by chemical processes. Examples of suitable chemical pretreatment processes include, for example, acid pretreatment by dilution, pretreatment by lime, wet oxidation, ammonia fiber / freeze blast (AFEX), ammonia percolation (APR), and pretreatment -organosolvent treatments.
[0208] In one embodiment, mild acid pretreatment or dilution is employed. Cellulosic material can be mixed with a diluted acid and water to form a suspension, heated by steam to the desired temperature, and after a residence time flashed up to atmospheric pressure. Suitable acids for this pretreatment method can include, for example, sulfuric acid, acetic acid, citric acid, nitric acid, phosphoric acid, tartaric acid, succinic acid, hydrogen chloride, or mixtures thereof. In a preferred variant, sulfuric acid is used. Diluted acid treatment can be conducted in a pH range of 1-5, a range of pH 1-4, or a range of pH 1-3. The acid concentration can be in the range of 0.01 to 20% by weight of acid, acid 0.05 to 10% by weight, acid 0.1 to 5% by weight, or 0.2 to 2.0 % by weight of acid. The acid is contacted with the cellulosic material, and can be carried out at a temperature in the range of 160-220 0 C, or 165-195 ° C, for a period of time ranging from a few seconds to minutes (for example, 1 second to 60 minutes). Pretreatment with dilute acid can be performed with a number of reactor models, including, for example, plug-reactors, counter-current, counter-current flow and shrinking continuous bed reactors. See Duff and Murray (1996), supra; Schell et al, Bioresource Technol, 91: 179-188 (2004); Lee et al., Adv. Biochem. Eng. Biotechnol., 65: 93-115 (1999).
[0209] In another embodiment, an alkaline pretreatment can be employed. Examples of suitable alkaline pretreatments include, for example, lime pretreatment, wet oxidation, ammonia percolation (APR), and ammonia fiber / freeze blast (AFEX). Pre-treatment with lime can be carried out with calcium carbonate, sodium hydroxide, ammonia or at temperatures of 85 ° C to 150 ° C, and in residence times of 1 hour to several days. See Wyman et al, Bioresource Technol, 96: 1959-1966 (2005); Mosier et al, Bioresource Technol, 96: 673-686 (2005).
[0210] In yet another embodiment, wet oxidation can be employed. Wet oxidation is a heat pretreatment that can be carried out, for example, at 180 ° C to 200 C for 5-15 minutes, with the addition of an oxidizing agent such as hydrogen peroxide or oxygen overpressure. See Schmidt and Thomsen, Bioresource Technol, 64: 139-151 (1998); Palonen et al., AppI. Biochem. Biotechnol, 117: 1-17 (2004); Varga et al, Biotechnol. Bioeng, 88: 567- 574 (2004). Martin et al, J. Chem. Technol. Biotechnol, 81: 1669-1677 (2006). Wet oxidation can be carried out, for example, on 1-40% dry matter, 2-30% dry matter, or 5-20% dry matter, and the initial pH can be increased by adding alkali (for example, sodium carbonate). A modification of the wet oxidation pre-treatment method may be 30% dry matter. In the wet explosion, the oxidizing agent can be introduced during the pre-treatment after a certain residence time, and the pre-treatment can end intermittently for atmospheric pressure. See WO 2006/032282.
[0211] In yet another embodiment, pretreatment methods using ammonia can be employed. See, for example, WO 2006/110891; WO 2006/11899; WO 2006/11900; and WO 2006/110901. For example, ammonia blast fiber (AFEX) involves the treatment of cellulosic material with liquid or gaseous ammonia at temperatures, for example, 17-20 bar) for a given period (for example, 5-10 minutes), where the content of matter drought can be, in some cases, as high as 60%. See Gollapalli et al., Appl. Biochem. Biotechnol., 98: 23-35 (2002); Chundawat et ah, Biotechnol. Bioeng, 96: 219-231 (2007); Alizadeh et al., Appl. Biochem. Biotechnol., 121: 1133-1141 (2005); . Teymouri et ah, Bioresource Technol, 96: 2014-2018 (2005). AFEX pretreatment can depolymerize cellulose, hemicellulose partial hydrolysis, and, in some cases, cleave some lignin-carbohydrate complexes. Pretreatment with Organosolvents
[0212] An organosolvent solution can be used to delignify cellulosic material. In one embodiment, an organosolvent pretreatment involves extraction with aqueous ethanol (eg 40-60% ethanol) at an elevated temperature (eg 160-200 0 C) over a period of time (eg 30 -60 minutes). See Pan et al, Biotechnol. Bioeng, 90: 473-481 (2005); Pan et al, Biotechnol. Bioeng, 94: 851-861 (2006); Kurabi et al., Appl. Biochem. Biotechnol, 121: 219-230 (2005). In one variation, sulfuric acid is added to the organosolvent solution as a catalyst to delignify cellulosic material. A person skilled in the art will recognize that an organosolvent pretreatment can typically separate most of the hemicellulose. Physical pretreatment
[0213] Physical pretreatment of cellulosic materials can promote the separation and / or release of cellulose, hemicellulose, and / or lignin by physical processes. Examples of suitable physical pretreatment processes may involve irradiation (for example, microwave irradiation), vapor / explosion steam, hydrothermolysis and combinations thereof.
[0214] physical pretreatment may involve high pressure and / or high temperature. In one embodiment, the physical pre-treatment is a steam explosion. In some variations, high pressure refers to a pressure in the range of 300 - 600 psi, 350 - 550 psi, or 400 - 500 psi, or about 450 psi. In some variations, it refers to high temperature at temperatures in the range of 100 - 300 0 C, or 140 - 235 ° C.
[0215] In another embodiment, the physical pretreatment is a mechanical pretreatment. Suitable examples of mechanical pretreatment can include various types of grinding or grinding (for example, dry grinding, wet grinding or vibrating ball grinding). In some variations, the mechanical pretreatment is carried out in a batch process, such as in a steam gun hydrolyzer system that uses high pressure and high temperature (for example, a Sunds Hydrolyzer available from Sunds Defibrator AB, Sweden ). Combined Physical and Chemical Pretreatment
[0216] In some embodiments, the cellulosic material can be pretreated chemically and physically. For example, in a variation, the pre-treatment step may involve treatment with dilute or mild acid and treatment at high temperature and / or pressure. It should be understood that physical and chemical pretreatments can be carried out sequentially or simultaneously. In another variation, pretreatment may also include mechanical pretreatment, in addition to chemical pretreatment. Biological pretreatment
[0217] Biological pretreatment techniques may involve the application of lignin-solubilizing microorganisms. See, for example, Hsu, T.-A., Pretreatment of Biomass, in Handbook on Bioethanol: Production and Utilization, Wyman, C. E., ed., Taylor & Francis, Washington, D.C., 179-212 (1996); Ghosh and Singh, Physicochemical and biological treatments for enzymatic / microbial conversion of cellulosic biomass, Adv. Appl. Microbiol., 39: 295 - 333 (1993); McMillan, JD, Pretreating lignocellulosic biomass: a review, in Enzymatic Conversion of Biomass for Fuels Production, Himmel, ME, Baker, J. 0., and Overend, RP, eds., ACS Symposium Series 566, American Chemical Society, Washington, DC, chapter 15 (1994); Gong, CS, Cao, NJ, Du, J., and Tsao, GT, Ethanol production from renewable resources, in Advances in Biochemical Engineering / Biotechnology, Scheper, T., ed., Springer- Verlag Berlin Heidelberg, Germany, 65: 207 - 241 (1999); Olsson and Hahn-Hagerdal, Fermentation of lignocellulosic hydrolysates for ethanol production, Enz. Microb. Tech., 18: 312 - 331 (1996); and Vallander and Eriksson, Production of ethanol from lignocellulosic materials: State of the art, Adv. Biochem. Eng./Biotechnol., 42: 63-95 (1990). In some embodiments, pretreatment can be carried out in an aqueous suspension. In other embodiments, the cellulosic material is present during pretreatment in amounts between 10 - 80 by weight, between 20 - 70 by weight, or between 30 - 60 by weight, or about 50% by weight. In addition, after pre-treatment, the pre-treated cellulosic material can be unwashed or washed using any method known in the art (for example, washed with water) before hydrolysis to produce one or more sugars or use with the polymeric acid catalyst. c) Saccharification
[0218] Saccharification is normally performed in agitated tank reactors or vessels under controlled pH, temperature and mixing conditions. A person skilled in the art will recognize that the appropriate processing time, temperature and pH conditions may vary depending on the type and quantity of cellulosic material, polymeric acid catalyst and the solvent used. These factors are described in more detail below. Processing of time, temperature and pH conditions
[0219] In some embodiments, saccharification can last up to 200 hours. In another embodiment, saccharification can take 1 to 96 hours, 12 to 72 hours, or 12 to 48 hours.
[0220] In some embodiments, saccharification is carried out at a temperature in the range of about 25 ° C to about 150 ° C. In other embodiments, saccharification is carried out at a temperature in the range of about 30 ° C at approximately 125 ° C, or about 80 ° C to about 120 ° C, or about 100 ° C to 110 ° C.
[0221] The pH for saccharification is generally affected by the intrinsic properties of the polymeric acid catalyst used. In particular, the acidic portion of the polymeric acid catalyst can affect the pH of saccharification. For example, the use of a portion of sulfuric acid in a polymeric acid catalyst results in saccharification at a pH of about 3. In other embodiments, saccharification is performed at a pH between 0 and 6. The reacted effluent typically has a pH of at least 4, or a pH value that is compatible with other processes, such as enzymatic treatment. It should be understood, however, that the pH can be modified and controlled by adding acids, bases or buffers.
[0222] In addition, the pH may vary within the reactor. For example, high acidity on or near the surface of the catalyst can be observed, while the regions distal to the surface of the catalyst can have a substantially neutral pH. Thus, a technician skilled in the subject would recognize that determining the pH of the solution must explain such spatial variation.
[0223] It should also be understood that, in certain embodiments, the saccharification methods described herein may also include monitoring the pH of the saccharification reaction, and optionally adjusting the pH within the reactor. In some cases, such as a low pH in the solution may indicate an unstable polymeric acid catalyst, where the catalyst may be the loss of at least a portion of its acid groups to the surrounding environment through leaching. In some embodiments, the pH near the surface of the polymeric acid catalyst is less than about 7, less than about 6, or below about 5. Amount of cellulosic material used
[0224] The amount of cellulosic material used in the methods described here in relation to the amount of solvent used can affect the reaction rate and yield. The amount of cellulosic material used can be characterized by the dry solids content. In certain embodiments, the dry solids content refers to the total solids in a paste as a percentage, on a dry weight basis. In some embodiments, the content of dry solid cellulosic materials ranges from about 5 by weight to about 95 by weight, between about 10% by weight to about 80% by weight, between about 15 to about 75% by weight weight, or between about 15 to about 50% by weight. Amount of polymeric acid catalyst used
[0225] The amount of polymeric acid catalysts used in the methods described here for saccharification may depend on several factors including, for example, the type of cellulosic material, the concentration of cellulosic material, the type and number of pre-treatment (s) applied for cellulosic material, and reaction conditions (for example, temperature, time and pH). In one embodiment, the weight ratio of the polymeric acid catalyst to the cellulose material is about O.lg / g to about 50 g / g, about 0. lg / g to about 25 g / g, about 0 , 1 g / g about 10 g / g, about 0.1 g / g about 5 g / g, about 0.1 g / g about 2 g / g, about 0.1 g / ga about 1 g / g, or about 0.1 to about 1.0 g / g. Solvent
[0226] In certain embodiments, hydrolysis using the polymeric acid catalyst is carried out in an aqueous medium. A suitable aqueous solvent is water, which can be obtained from a variety of sources. In general, water sources with lower concentrations of ionic species are preferable, since such ionic species can reduce the effectiveness of the polymeric acid catalyst. In some embodiments in which the aqueous solvent is water, water has less than 10% ionic species (for example, sodium salts, phosphorus, ammonium, magnesium, or other species naturally found in lignocellulosic biomass).
[0227] In addition, as the cellulosic material is hydrolyzed, water is consumed on a mol by mol basis with the sugars produced. In certain embodiments, the saccharification methods described herein may further include monitoring the amount of water present in the saccharification reaction and / or the ratio of water to biomass, over a period of time. In other embodiments, the saccharification methods described herein may further include providing water directly for the reaction, for example, in the form of steam or condensed steam. For example, in some embodiments, the hydration conditions in the reactor are such that the water-to-cellulosic material ratio is 5: 1, 4: 1, 3: 1, 2: 1, 1: 1, 1 : 2, 1: 3, 1: 4, or 1: 5, or less than 1: 5. It should be understood, however, that the ratio of water to cellulosic material can be adjusted based on the specific polymeric acid catalyst used. Batch versus continuous processing
[0228] In general, the polymeric acid catalyst and cellulosic materials are introduced into an inner chamber of a reactor, either simultaneously or sequentially. Saccharification can be carried out in a batch process or in a continuous process. For example, in one embodiment, saccharification is carried out in a batch process, where the contents of the reactor are continuously mixed or homogenized, and all or a substantial amount of the reaction products are removed. In a variant, saccharification is performed in a discontinuous process, in which the contents of the reactor are initially mixed or agitated, but no more physical mixing is carried out. In another variation, saccharification is performed in a discontinuous process, in which once again the mixing of the contents, or the periodic mixing of the contents of the reactor is performed (for example, at one or more times per hour), all or once substantial amount of the reaction products are removed after a certain period of time.
[0229] In other embodiments, saccharification is carried out in a continuous process, in which the content flows through the reactor with an average rate of continuous flow, but without explicit mixing. After the introduction of the polymeric acid catalyst and cellulosic materials in the reactor, the reactor contents are continuously or periodically mixed or combined, and after a period of time, less than all reaction products are removed. In a variant, saccharification is carried out in a continuous process, in which the mixture containing the catalyst and the biomass is not actively mixed. In addition, the catalyst and biomass mixing can occur as a result of the redistribution of gravity settling polymeric acid catalysts, or the non-active mixing that occurs as the material flows through a continuous reactor. Reactors
[0230] The reactors used for the saccharification methods described here can be open or closed reactors suitable for use in containing the chemical reactions described here. Suitable reactors may include, for example, a batch-fed agitated reactor, a batch-agitated reactor, a continuous flow agitated reactor with ultrafiltration, a continuous piston column flow reactor, a friction reactor, or a stirred reactor intensity induced by an electromagnetic field. See, for example, Fernanda de Castilhos Corazza, Flavio Faria de Moraes, Gisella Maria Zanin and Ivo Neitzel, Optimal control in fed-batch reactor for the cellobiose hydrolysis, Acta Scientiarum. Technology, 25: 33-38 (2003); Gusakov, A. V., and Sinitsyn, A. P., Kinetics of the enzymatic hydrolysis of cellulose: 1. A mathematical model for a batch reactor process, Enz. Microb. Technol., 7: 346-352 (1985); Ryu, S. K., and Lee, J. M., Bioconversion of waste cellulose by using an attrition bioreactor, Biotechnol. Bioeng. 25: 53-65 (1983); Gusakov, A. V., Sinitsyn, A. P., Davydkin, I. Y., Davydkin, V. Y., Protas, O. V., Enhancement of enzymatic cellulose hydrolysis using a novel type of bioreactor with intensive stirring induced by electromagnetic field, Appl. Biochem. Biotechnol., 56: 141-153 (1996). Other types of suitable reactors may include, for example, fluidized bed reactors, upward flow blankets, immobilized reactors and type of extruder for hydrolysis and / or fermentation.
[0231] In certain embodiments, where saccharification is performed as a continuous process, the reactor may include a continuous mixer, such as a screw mixer. Reactors can generally be manufactured from materials that are capable of withstanding the physical and chemical forces exerted during the processes described here. In some embodiments, the materials used for the reactor are able to tolerate high concentrations of liquid strong acids; however, in other embodiments, such materials cannot be resistant to strong acids.
[0232] In addition, the reactor typically contains an outlet for the removal of contents (for example, a solution containing sugar) from the reactor. Optionally, these output means are connected to a device capable of processing the content taken from the reactor. Alternatively, the contents are removed stored. In some embodiments, the outlet means of the reactor are connected to a continuous incubator in which the contents are introduced reacted. The reactor can be filled with biomass by an upper load feeder that contains a hopper capable of maintaining the biomass. In addition, the outlet means provide for the removal of residual biomass by, for example, a screw feeder, by gravity, or a low shear screw.
[0233] It should also be understood that additional cellulosic material and / or catalyst can be added to the reactor, either at the same time or one after the other. Saccharification Rate and Yield
[0234] The use of the polymeric acid catalysts described here can increase the rate and / or the yield of saccharification. The ability of the polymeric acid catalyst to hydrolyze the cellulose and hemicellulose components of biomass to soluble sugars can be measured by determining the constant effective first order rate,
Where Δt is the duration of the reaction and X is the extent of the reaction for species i (for example, glucan, xylan, arabinan). In some embodiments, the polymeric acid catalysts described herein are capable of degrading the biomass into one or more sugars to a first order velocity constant of at least 0.001 per hour, at least 0.01 per hour, at least 0, 1 per hour, at least 0.2 per hour, at least 0.3 per hour, at least 0.4 per hour, at least 0.5 hour, or at least 0.6 per hour.
[0235] The yield of the hydrolysis of the cellulose and hemicellulose components of the biomass to soluble sugars by the acid catalyst of the polymer can be measured by determining the degree of polymerization of the residual biomass. The lower the degree of polymerization of the residual biomass, the greater the hydrolysis yield. In some embodiments, the polymeric acid catalysts described herein are capable of converting biomass into one or more sugars and residual biomass, wherein the residual biomass has a degree of polymerization of less than 300, less than 250, less than 200, less than 150, less than 100, less than 90, less than 80, less than 70, less than 60, or less than 50. d) Separation and purification of sugars
[0236] In some embodiments, the method for degrading cellulosic material using the polymeric acid catalysts described herein further includes recovering the sugars that are produced from the hydrolysis of the cellulosic material. In another embodiment, the method for degrading cellulosic material using the polymeric catalyst described herein further includes recovering the degraded or converted cellulosic material.
[0237] Sugars, which are typically soluble, can be separated from residual insoluble cellulosic material using technology well known in the art, such as, for example, centrifugation, filtration, decantation and gravity.
[0238] Separation of sugars can be carried out in the hydrolysis reactor, or in a separating vessel. In an exemplary embodiment, the method for degrading cellulosic material is carried out in a system with a hydrolysis reactor and a separation tank. Effluent from the reactor containing the monosaccharides and / or oligosaccharides is transferred to a separation vessel and is washed with a solvent (for example, water), by adding the solvent inside the separating vessel and then separating the solvent in a centrifuge to be continued. Alternatively, in another exemplary embodiment, a reactor effluent containing residual solids (for example, residual cellulosic materials) is removed from the reaction vessel and washed, for example, transmitting the solids on a porous base (for example, a mesh belt) by means of a solvent (eg water) wash flow. After contact of the current with the reacted solids, a liquid phase containing the monosaccharides and / or oligosaccharides is generated. Optionally, the residual solids can be separated by a cyclone. Suitable types of cyclones used for separation can include, for example, tangential cyclones, sparks and rotary separators and multi-axial and cyclone units.
[0239] In another embodiment, the separation of sugars is carried out by batch or continuous differential sedimentation. Effluent reactor is transferred to a separation vessel, optionally combined with water and / or enzymes for further treatment of the effluent. Over a period of time, solid biomaterials (e.g., treated residual biomass), the solid catalyst, and the aqueous sugar-containing material can be separated by differential sedimentation in a plurality of phases (or layers). Generally, the catalyst layer can settle to the bottom, and, depending on the density of the residual biomass, the biomass phase can be on top of, or below, the aqueous phase. When the separation phase is carried out in a discontinuous manner, the phases are removed sequentially, either from the top of the container or from an outlet at the bottom of the vessel. When the separation phase is carried out continuously, the separation container contains one or more than one outlet means (for example, two, three, four, or more than four), usually located in different vertical planes in the side wall of the vessel separation, such that one, two, or three phases are removed from the vessel. The removed phases are transferred to subsequent vessels or other storage media. Through these processes, a person skilled in the art would be able to capture (1) the catalyst layer and the separate biomass or aqueous layer, or (2) the aqueous catalyst and the biomass layers separately, allowing for effective recycling catalyst, biomass retreatment, and sugar separation. In addition, the control of the phase removal rate and other parameters allows a greater recovery efficiency of the catalyst. Subsequent to the removal of each of the separate phases, the catalyst and / or biomass can be washed separately by the aqueous layer to remove adhered sugar molecules.
[0240] Sugars isolated from the container can be subjected to additional processing steps (for example, such as drying, fermentation) for the production of biofuels and other bioproducts. In some embodiments, the monosaccharides that are isolated can be at least 1% pure, at least 5% pure, at least 10% pure, at least 20% pure, at least 40% pure, at least 60% pure, at least 80% pure, at least 90% pure, at least 95% pure, at least 99% pure, or greater than 99% pure, as determined by analytical procedures known in the art, such as determination by liquid chromatography of high efficiency (HPLC), functionalization and analysis by gas chromatography, mass spectrometry, based on spectrophotometric procedures, chromophore complexation and / or carbohydrate oxidation-reduction chemistry.
[0241] Residual biomass isolated from pots can be useful as a combustion fuel or as a source of food for non-human animals, such as livestock. Compositions containing polymeric acid catalyst
[0242] Compositions involving polymeric acid catalysts which can be used in a variety of methods described herein, including the decomposition of cellulosic material, are also provided herein.
[0243] In one aspect, compositions are provided which include biomass, and the polymeric acid catalysts described herein. In some embodiments, the composition additionally includes a solvent (for example, water). In some embodiments, the biomass includes cellulose, hemicellulose, or a combination thereof.
[0244] In yet another aspect, compositions are provided which include the polymeric acid catalysts described herein, one or more sugars and residual biomass. In some embodiments, the one or more sugars and one or more monosaccharides, one or more oligosaccharides, or a mixture thereof. In certain embodiments, the one or more sugars are two or more sugars that comprise at least one C4-C6 monosaccharide and at least one oligosaccharide. In one embodiment, the one or more sugars are selected from the group consisting of glucose, galactose, fructose, xylose and arabinose. Intermediate Catalyst
[0245] When polymeric acid catalysts are used to degrade cellulosic materials, as described above, a catalytic intermediate is formed. Provided here are also the catalytic intermediates, in which the polymeric acid catalyst coordinates with the cellulosic material. The acid catalyst can be polymeric for cellulose and / or hemicellulose to break down cellulosic material to produce hydrogen bonded monosaccharides and oligosaccharides.
[0246] The ionic portion of polymeric acid catalysts can help break down the tertiary structure of cellulosic materials. In some embodiments, the ionic portion can disrupt the inter- and intra-molecular hydrogen bonding in polysaccharide materials. The disruption of the hydrogen bond of the tertiary structure may allow the acidic moiety to more easily access the glycosidic bonds of the polysaccharides. In other embodiments, the acidic portion can disturb the glycosidic bonds of the polysaccharides. Therefore, the combination of the two functional portions on a single polymer can provide a catalyst that is effective in the breakdown of polysaccharides, using relatively mild conditions, compared to methods that employ a more corrosive acid, or methods that employ severe conditions such as high temperatures and pressure.
[0247] In certain embodiments, in the intermediate saccharification, the ionic radical of the polymer is hydrogen-bonded to the alcohol carbohydrate groups present in cellulose, hemicellulose, and other components that contain biomass oxygen. In certain embodiments, in intermediate saccharification, the acid portion of the polymer is for the carbohydrate alcohol groups present in cellulose, hemicellulose, and other components that contain lignocellulosic biomass oxygen, including the glycosidic bonds between the hydrogen bonded sugar monomers. Without wishing to be bound by any theory, in certain embodiments of intermediate saccharification, the hydrogen bonds between an exemplary polymer and the alcohol carbohydrate groups present in the biomass can be as illustrated in FIG. 9. Downstream products. a) Fermentation of isolated sugars
[0248] The sugars obtained from the hydrolysis of cellulosic material can be used in downstream processes for the production of biofuels and other bio-based chemicals. In another aspect, one or more sugars obtained from the hydrolysis of the cellulosic material using the polymeric acid catalyst described herein can be fermented to produce one or more products downstream (for example, ethanol and other biofuels, vitamins, lipids, proteins).
[0249] In some embodiments, saccharification can be combined with a separate fermentation or in a simultaneous process. The fermentation can use the aqueous sugar phase or, if the sugars are not substantially purified from the reacted biomass, the fermentation can be carried out on an impure mixture of sugars and reacted biomass. Such methods include, for example, separate and fermentation hydrolysis (SHF), simultaneous saccharification and fermentation (SSF), simultaneous saccharification and co-fermentation (SSCF), hybrid hydrolysis and fermentation (HHF), separate and co-fermentation hydrolysis (SHCF), hybrid hydrolysis and co-fermentation (HHCF), and direct microbial conversion (DMC).
[0250] For example, SHF uses process steps separate from the first cellulosic material to enzymatically hydrolyze into fermentable sugars (eg, glucose, cellobiose, cellotriose, and pentose sugars), and then ferment them to ethanol.
[0251] In SSF, the enzymatic hydrolysis of cellulosic material and the fermentation of sugars in ethanol are combined in a single step. See Philippidis, GP, Cellulose bioconversion technology, in the Handbook on Bioethanol: Production and Use, Wyman, CE, ed, Taylor & Francis, Washington, DC, 179-212 (1996).
[0252] SSCF involves the co-fermentation of various sugars. See Sheehan, J., and Himmel, M., Enzymes, energy and the environment: a strategic perspective on the United States Department of Energy research and development activities for bioethanol, Biotechnol. Prog., 15: 817-27 (1999).
[0253] HHF involves a separate hydrolysis step, and, in addition, a simultaneous saccharification and hydrolysis step, which can be carried out in the same reactor. The steps in an HHF process can be performed at different temperatures; for example, enzymatic saccharification at elevated temperature followed by SSF, at a temperature lower than the fermentation stress can tolerate.
[0254] DMC combines all three processes (enzyme production, hydrolysis, and fermentation) in one or more stages, where the same organism is used to produce the enzymes for converting cellulosic material into fermentable sugars and to convert the fermentable sugars in a final product. See Lynd, LR, Weimer, PJ, van Zyl, WH, and Pretorius, IS, the use of microbial cellulose: Fundamentals and biotechnology, Microbiol. Mol. Biol. Comments, 66: 506-577 (2002). General methods of preparing polymeric acid catalysts
[0255] The polymers described herein can be prepared using polymerization techniques known in the art, including, for example, techniques for initiating the polymerization of a plurality of monomer units.
[0256] In some embodiments, the polymers described herein can be formed by first forming a polymer intermediate functionalized with the ionic group, but it is free or substantially free of the acid group. The intermediate polymer can then be functionalized with the acid group.
[0257] In other embodiments, the polymers described herein can be formed by first forming a polymer intermediate functionalized with the acid group, but it is free or substantially free of the ionic group. The intermediate polymer can then be functionalized with the ionic group.
[0258] In still other embodiments, the polymers described herein can be formed by polymerizing monomers with both acidic and ionic groups.
[0259] Also provided here are such intermediate polymers, including those obtained at different points within a synthetic route to produce the fully functionalized polymers described herein. In some embodiments, the polymers described herein can be made, for example, on a scale of at least 100 g, or at least 1 kg, in a discontinuous or continuous process. EXAMPLES Preparation of Polymeric Materials
[0260] Unless otherwise indicated, commercial reagents were obtained from Sigma-Aldrich, St. Louis, MO, USA, and were purified before use according to Perrin and Armarego's guidelines. See Perrin, DD & Armarego, WLF, Purification of Laboratory Chemicals, 3rd ed .; Pergamon Press, Oxford, 1988. The nitrogen gas for use in chemical reactions was of ultra-pure quality, and was dried by passing through a drying tube containing phosphorus pentoxide. Unless otherwise indicated, all non-aqueous reagents were transferred under an inert atmosphere via a syringe or Schlenk vial. The organic solutions were concentrated under reduced pressure on a Buchi rotary evaporator. Whenever purification is necessary, chromatography of reagents or products was performed using forced flow chromatography on 60 mesh silica gel according to the method described by Still et al., See Still et al, J. Org. Chem. , 43: 2923 (1978). Thin layer chromatography (TLC) was performed using silica coated glass plates. The chromatogram developed was visualized using cerium molybdate dye (ie Hanessian) or KMnO-j dye, with gentle heating, as needed. Spectroscopic Fourier-Transform Infrared (FTIR) analysis of solids samples was performed on a Perkin-Elmer 1600 instrument equipped with a horizontal attenuated total reflection coefficient (ATR) using a Selenide zinc crystal (ZnSe). Example 1: Preparation of poly [styrene-co-vinylbenzylchloro-co-divinylbenzene]
[0261] To a 500 ml round bottom flask (RBF) containing a stirred solution of 1.08 g of poly (vinyl alcohol) in 250.0 ml of deionized H2O at 0 0 C, a solution gradually containing 50.04 g (327.9 mmol) of vinylbenzyl chloride (mixture of 3- and 4- isomers), 10.13 g (97.3 mmol) of styrene, 1.08 g (8.306 mmol) of divinylbenzene (DVB , mixture of 3- and 4-isomers) and 1.507 g (9.2 mmol) of azobisisobutyronitrile (AIBN) in 150 mL of a 1: 1 (by volume) benzene / tetrahydrofuran (THF) mixture at 0 0 C After 2 hours of stirring at 0 ° C to homogenize the mixture, the reaction flask was transferred to an oil bath to increase the reaction temperature to 75 ° C, and the mixture was stirred vigorously for 28 hours. The resulting polymer beads were vacuum filtered through a glass frit funnel to collect the polymer product. The beads were washed several times with 20% (by volume) of methanol in water, THF and MeOH, and dried overnight at 50 ° C under reduced pressure to obtain 59.84 g of polymer. The polymer beads were separated by size using 100, 200, and 400 mesh sizes. Example 2: Preparation of poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1 -ium-chloride-co-divinylbenzene]
[0262] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 50 g, 200 mmol) was loaded into a 500 ml three-necked flask (TNF) , equipped with a mechanical stirrer, a dry nitrogen line, and a bleed valve. Dry dimethylformamide (185 ml) was added to the flask (via a cannula under N2 atmosphere) and stirred to form a viscous polymer resin paste. 1-methylimidazole (36.5 g, 445 mmol) was then added and stirred at 95 ° C for 8 h. After cooling, the reaction mixture was filtered using a vacuum-fried glass funnel, washed sequentially with deionized water and ethanol, and finally air dried.
[0263] The chemical functionalization of the polymer material, expressed in millimoles of functional groups per gram of dry polymer resin (mmol / g) was determined by ion exchange titration, for the determination of acid cation exchange protons, a mass known dryness of the polymer resin was added to a saturated aqueous solution of sodium chloride and titrated with a standard solution of sodium hydroxide to the end point of phenolphthalein. For the determination of the ionic chloride ion exchange content, a known dry mass of the polymer resin was added to an aqueous sodium nitrate solution and neutralized with sodium carbonate. The resulting mixture was titrated with a standardized solution of silver nitrate to the potassium chromate terminal. For polymeric materials in which the exchangeable anion was not chloride, the polymer was treated first by stirring the material in aqueous hydrochloric acid, followed by washing with water several times until the effluent was neutral (as determined by pH paper). The chemical functionalization of the polymer resin with methylimidazolium chloride groups was determined to be 2.60 mmol / g by means of gravimetry and 2.61 mmol / g by means of titration. Example 3: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-ium-bisulfate -co-divinylbenzene]
[0264] Poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-iumchloro-co-divinylbenzene] (63 g) was loaded into a 500 ml flask equipped with a magnetic stirring and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4, 300 ml) was gradually added to the flask under agitation, which resulted in the formation of a dark red resin paste. The slurry was stirred at 85 ° C for 4 h. After cooling to room temperature, the reaction mixture was filtered using a vacuum-funneled glass funnel and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 1.60 mmol / g, as determined by titration following the procedure of Example 2. Example 4: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid - co-3-methyl-1- (4-vinylbenzyl) divinylbenzene 1-one co-chloride — 3H-imidazole]
[0265] Poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1 - (4-vinylbenzyl) -3H-imidazol-1-yo-bisulfate codivinylbenzene] (sample of example 3), contained in the glass of fried funnel, was washed several times with a 0.1 M HQ solution to ensure complete exchange of HSO4- with Cl-. The resin was then washed with deionized water until the effluent was neutral, as determined by pH paper. The resin was finally air dried. Example 5: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole 1 -ium acetate-co - divinylbenzene]
[0266] The suspension of poly [styrene-co- 4-vinylbenzenesulfonic acid-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-yo-bisulfate-co-divinylbenzene] (sample from example 3 ) in 10% aqueous acetic acid solution was stirred for 2 h at 60 ° C to ensure complete exchange of HSO4- with AcO-. The resin was filtered using a fritted glass funnel and then washed several times with deionized water until the effluent was neutral. The resin was finally air dried. Example 6: Preparation of poly [styrene-co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole -1-io-chloride-co-divinylbenzene]
[0267] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a three-neck 250 (TNF) flask, equipped with a mechanical stirrer, a dry nitrogen line, and the bleed valve. Dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2 atmosphere) and stirred to give viscous resin paste. 1-ethylimidazole (4.3 g, 44.8 mmol) was then added to the resin suspension and stirred at 95 ° Cunder 8 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer resin with ethylimidazolium chloride groups was determined to be 1.80 mmol / g, as determined by titration following the procedure of Example 1. Example 7: Preparation of poly [styrene-co-4- acid vinylbenzenesulfonic-co-3-ethyl-1- (4-vinylbenzyl) -3H- imidazole-1-yo-bisulfate - co-divinylbenzene]
[0268] Poli [styrene-co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene] (5 g) was loaded into a 100 ml flask equipped with an agitator magnetic and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4 45 mL) was gradually added to the flask under agitation, which resulted in the formation of a uniform dark red resin slurry. The slurry was stirred at 95 - 100 ° C for 6 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 1.97 mmol / g, as determined by titration following the procedure of Example 2. Example 8: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid -co- 3-ethyl-1- (4-vinylbenzyl) - 3H- imidazole 1-co-divinylbenzene chloride]
[0269] Poly resin beads [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-yo-bisulfate codivinylbenzene] (sample 7) contained in the sintered glass funnel glass it was washed several times with a 0.1 M HQ solution to guarantee the complete exchange of HSOr with Cl ". The resin was then washed with deionized water until the effluent was neutral, as determined by paper pH The resin was finally washed with ethanol and air dried Example 9: Preparation of poly [styrene-co-1- (4-vinylbenzyl) -3H-imidazol-1-chloro-co-divinylbenzene]
[0270] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Chloroform (50 ml) was added to the flask and stirred to form resin paste. Imidazole (2.8 g, 41.13 mmol) was then added to the resin slurry and stirred at 40 ° C for 18 h. After the reaction was completed, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer resin with imidazolium chloride groups was determined to be 2.7 mmol / g, as determined by titration following the procedure of Example 2. Example 10: Preparation of poly [styrene-co-4- acid vinylbenzenesulfonic-co- 1- (4-vinylbenzyl) -3H-imidazole-1-io-bisulfate-co-divinylbenzene]
[0271] Poly [styrene-co-1- (4-vinylbenzyl) -3H-imidazole-1-chloro-co-divinylbenzene] (5 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, 80 mL H2SO4) was gradually added to the flask and stirred to form the dark red resin slurry. The slurry was stirred at 95 ° C for 8 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The beads were finally sulfonated, washed with ethanol and air dried. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 1.26 mmol / g, as determined by titration following the procedure of Example 2. Example 11: Preparation of poly [styrene-co-3-methyl-1 - (4-vinylbenzyl) -3H-benzoimidazole-1-chloro-co-divinylbenzene]
[0272] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl * = density of ~ 4.0 mmol / g, 4 g, 16 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dry dimethylformamide (50 ml) was added to the flask (via a cannula under N2 atmosphere) and stirred to form a viscous polymer resin paste. 1-methylbenzimidazole (3.2 g, 24.2 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 18 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer with methylbenzimidazolium chloride groups was determined to be 1.63 mmol / g, as determined by titration following the procedure of Example 2. Example 12: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co-3 acid -methyl-l- (4-vinylbenzyl) -3H- benzoimidazole-1-yo-bisulfate-co-divinylbenzene]
[0273] Poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-i-co-divinylbenzene chloride] (5.5 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4, 42 ml) and smoking sulfuric acid (20% free SO3, 8 ml) was gradually added to the flask and stirred to form the dark red resin paste. The slurry was stirred at 85 ° C for 4 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The beads were finally sulfonated, washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 1.53 mmol / g, as determined by titration following the procedure of Example 2. Example 13: Preparation of poly [styrene-co-1- (4-vinylbenzyl) -pyridinium chloride-co-divinylbenzene]
[0274] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 5 g, 20 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dry dimethylformamide (45 ml) was added to the flask (via a cannula under N2) while stirring and, consequently, the uniform viscous paste of the polymer resin was obtained. Pyridine (3 mL, 37.17 mmol) was then added to the resin slurry and stirred at 85-90 ° C for 18 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer resin with pyridinium chloride groups was determined to 3.79 mmol / g, as determined by titration following the procedure of Example 2. Example 14: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co acid - 1- (4-vinylbenzyl) -pyridinium-bisulfate-co-divinylbenzene]
[0275] Poly [styrene-co-1- (4-vinylbenzyl) -pyridinium-co-divinylbenzene] resin beads (4g) were loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98% w / w, H2SO4 45 mL) was gradually added to the flask under agitation, consequently, which resulted in the formation of a uniform dark red resin slurry. The slurry was heated to 95 - 100 ° C, with continuous stirring, for 5 h. After the reaction was completed, the cooled reaction mixture was filtered using a sintered glass funnel under vacuum and then washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The resin beads were finally washed with ethanol and air dried. The chemistry of the functionalization of the polymer with sulfonic acid groups was determined to be 0.64 mmol / g, as determined by titration following the procedure of Example 2. Example 15: Preparation of poly [styrene-co-1- (4-vinylbenzyl) ) -pyridinium-co-3-methyl-1- (4-vinylbenzyl) -3H- imidazole-1-chloro-co-divinylbenzene]
[0276] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2), while stirring which resulted in the formation of a viscous polymer resin paste. Pyridine (1.6 mL, 19.82 mmol) and 1-methylimidazole (1.7 mL, 21.62 mmol) were then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 18 h. After completion of the reaction, the reaction mixture was cooled, filtered through a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer with pyridinium chloride and 1-methylimidazole chloride groups was determined to be 3.79 mmol / g, as determined by titration following the procedure of Example 2. Example 16: Preparation of poly [styrene-co-acid] 4-vinylbenzenesulfonic-co-1- (4-vinylbenzyl) -pyridiniumchloro-co-3-methyl-1- (4-vinylbenzyl) bisulfate-3H-imidazol-1-io -co-divinylbenzene]
[0277] Poly [styrene-co-1- (4-vinylbenzyl) -pyridinium-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene] (5 g) a 100 ml flask equipped with a magnetic stir bar and condenser was loaded. Cold concentrated sulfuric acid (> 98 w / w, H2SO4 75 mL) and smoking sulfuric acid (20% free SO3, 2 mL) were then gradually added to the flask under agitation, therefore, which resulted in the formation of a dark resin paste red colored uniform. The slurry was heated to 95-100 ° C, under continuous stirring, for 12 h. After the reaction was completed, the reaction mixture was cooled and filtered using a sintered glass funnel under vacuum and then washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 1.16 mmol / g, as determined by titration following the procedure of Example 2. Example 17: Preparation of poly [styrene-co-4-methyl-4 - (4-vinylbenzyl) -morpholin-4-io co-divinylbenzene chloride]
[0278] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dry dimethylformamide (85 ml) was added to the flask (via a cannula under N2), while stirring which resulted in the formation of a uniform viscous paste from the polymer resin. 1-methylmorpholine (5.4 ml, 49.12mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 18 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer with methylmorpholinium chloride groups was determined to be 3.33 mmol / g, as determined by titration following the procedure of Example 2. Example 18: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid -co- 4 -methyl-4- (4-vinylbenzyl) morpholin-4-io bisulfate-co-divinylbenzene]
[0279] Poli [styrene-co-l-4-methyl-4- (4-vinylbenzyl) - morpholin-4-io-chloride-co-divinylbenzene] (8 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4 50 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a dark red paste. The slurry was stirred at 90 ° C for 8 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 1.18 mmol / g, as determined by titration following the procedure of Example 2.
[0280] Example 19: Preparation of [olystyrene-co-triphenyl (4-vinylbenzyl) -phosphonium chloro-co-divinylbenzene]
[0281] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl "= density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser, dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2), while stirring and the uniform viscous paste of the polymer resin was obtained, triphenylphosphine (11.6 g, 44.23mmol) was added ) and then was added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 18 h. After cooling, the reaction mixture was filtered using vacuum frit funnel, washed sequentially with deionized water and ethanol, and finally air dried The chemical functionalization of the polymer with triphenylphosphonium groups was determined to be 2.07 mmol / g, as determined by titration following the procedure of Example 2. Example 20: Preparation of poly [styrene acid -co-4-vinylbenzenesulfonic-co-triphenyl (4-vinylbe nzil) -phosphonium bisulfate-co-divinylbenzene]
[0282] The poly (styrene-co-triphenyl (4-vinylbenzyl) - chloro-co-divinylbenzene phosphonium) (7 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4 40 mL) and smoking sulfuric acid (20% free SO3, 15 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a dark red colored paste . The slurry was stirred at 95 ° C for 8 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 2.12 mmol / g, as determined by titration following the procedure of Example 2. Example 21: Preparation of poly [styrene-co-1- (4-vinylbenzyl) -piperidine-co-divinylbenzene]
[0283] The poly (styrene-co-vinylbenzyl chloride-co-divinylbenzene) (Cl "= density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a magnetic stirring and condenser, dry dimethylformamide (50 ml) was added to the flask (via a cannula under N2), while stirring which resulted in the formation of a uniform viscous paste from the polymer resin Piperidine (4 g, 46.98 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 16 h. After cooling, the reaction mixture was filtered using vacuum frit funnel, washed sequentially with deionized water. and ethanol, and finally air-dried Example 22: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1- (4-vinylbenzyl) -piperidine-co-divinylbenzene]
[0284] Poly [styrene-co-1- (4-vinylbenzyl) -piperidine-co-divinyl-benzene] (7 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4 45 mL) and smoking sulfuric acid (20% free SO3, 12 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a dark red colored paste. The slurry was stirred at 95 ° C for 8 h. After the reaction was completed, the cooled reaction mixture was filtered using a sintered glass funnel under vacuum and then washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 0.72 mmol / g, as determined by titration following the procedure of Example 2. Example 23: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co- 1-methyl-1- (4-vinylbenzyl) piperdin-1-i chloride-co-divinylbenzene]
[0285] The poly (styrene-co-4- (1-piperidine) methylstyrene-co-divinylbenzene) (4 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Dry dimethylformamide (40 ml) was added to the flask (via cannula under N2), with stirring, to obtain uniform viscous paste. Iodomethane (1.2 ml) and potassium iodide (10 mg) were then added to the flask. The reaction mixture was stirred at 95 ° C for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with diluted HCl solution to ensure complete exchange of T with Cl ". The resin was finally washed with deionized water until that the effluent be neutral, as determined by pH paper. The resin was finally air dried. Example 24: Preparation of poly [styrene-co-4- (4-vinylbenzyl) -morpholine-co-divinylbenzene]
[0286] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl - = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dimethylformamide under N2), while stirring and, consequently, the uniform viscous paste of the polymer resin was obtained. Morpholine (4 g, 45.92 mmol) was then added to the resin slurry and the resulting reaction mixture was heated to 95 ° C with continuous stirring for 16 h. After the reaction was completed, the reaction mixture was cooled, filtered through a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. Example 25: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co- 4- (4-vinylbenzyl) -morpholine-co-divinylbenzene]
[0287] Poly [styrene-co-4- (4-vinylbenzyl) -morpholine-co-divinyl-benzene] (10 g) was loaded into a 200 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2 SO4 90 mL) and smoking sulfuric acid (20% free SO3, 10 mL) was gradually added to the stirring flask, while, consequently, it resulted in the formation of a dark colored paste red. The slurry was stirred at 95 ° C for 8 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 0.34 mmol / g, as determined by titration following the procedure of Example 2. Example 26: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co- 4- (4-vinylbenzyl) -morpholine-oxide-4-co-divinylbenzene]
[0288] Poly [styrene-co-4-vinylbenzenesulfonic acid-co- 4- (4-vinylbenzyl) -morpholine benzene-co-divinyl] (6 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Methanol (60 ml) was then loaded into the flask, followed by the addition of hydrogen peroxide (30% solution in water, 8.5 ml). The reaction mixture was refluxed, under continuous stirring, for 8 h. After cooling, the reaction mixture was filtered, washed sequentially with deionized water and ethanol, and, finally, air dried. Example 27: Preparation of poly [styrene-co-4-vinyl benzyl-triethylammonium chloride-co-divinylbenzene]
[0289] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dimethylformamide under N2), while stirring and, consequently, the uniform viscous paste of the polymer resin was obtained. Triethylamine (5 mL, 49.41 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 18 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer resin with triethylammonium chloride groups was determined to be 2.61 mmol / g, as determined by titration following the procedure of Example 2. Example 28: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid -co- triethyl- (4-vinylbenzyl) -ammonium chloride-co-divinylbenzene]
[0290] Poly [styrene-co-triethyl- (4-vinylbenzyl) ammonium chlorocodevinylbenzene] (6 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2SO4 60 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a uniform dark red resin slurry. The slurry was stirred at 95 - 100 ° C for 8 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 0.31 mmol / g, as determined by titration following the procedure of Example 2. Example 29: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co- vinylbenzylchloro-co-divinylbenzene]
[0291] The poly (styrene-cO-vinylbenzyl chloride-codivinylbenzene) (6 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 25 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a dark red paste. The slurry was stirred at 90 ° C for 5 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 0.34 mmol / g, as determined by titration following the procedure of Example 2. Example 30: Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid -co- 3-methyl-1- (4-vinylbenzyl) -3H- imidazole 1-one co-divinylbenzene chloride]
[0292] Poly [styrene-co-4-vinylbenzenesulfonic-co-vinylbenzylchloro-codivinylbenzene] (5 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Dry dimethylformamide (20 ml) was added to the flask through a cannula under (N2), while stirring and the uniform viscous paste of the polymer resin was obtained. 1-methylimidazole (3 ml, 49.41 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 18 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with ionized water. The resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with groups of sulfonic acid and methylimidiazolium chloride groups was determined to be 0.23 mmol / g and 2.63 mmol / g, respectively, as determined by titration following the procedure of Example 2. Example 31: Preparation of poly [styrene-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazol-1-io-co-4 bornyl-1- (4-
[0293] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl- = density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2), while stirring and, consequently, the uniform viscous paste of the polymer resin was obtained. 4-pyridyl-boric acid (1.8 g, 14.6 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 2 days. 1-methylimidazole (3 ml, 49.41 mmol) was then added to the reaction mixture and stirred at 95 ° C for 1 day. After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemistry of functionalization of the polymer with the boronic acid group was determined to be 0.28 mmol / g, respectively, as determined by titration following the procedure of Example 2. Example 32; Preparation of poly [styrene-co-3-methyl-l- (4-vinylbenzyl) -3H-imidazol-1-10 co-chloride - 1 - (4-vinylphenyl) methylphosphonic acid-co-divinylbenzene]
[0294] Poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-i-co-divinylbenzene chloride] (Cl “= density of ~ 2.73 mmol / g, 5g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Triethylphosphite (70 ml) was added to the flask and the resulting suspension was stirred at 120 ° C for 2 days. The reaction mixture was filtered using a glass frit funnel and the resin beads washed repeatedly with deionized water and ethanol. These resin beads were then suspended in concentrated HQ (80 ml) and refluxed at 115 ° C under continuous stirring for 24 h. After cooling to room temperature, the reaction mixture was filtered using a porous glass funnel under vacuum and then washed several times with deionized water. The resin beads were finally washed with ethanol and air dried. The chemistry of the functionalization of the polymer with groups of phosphonic acid and methylimidiazolium chloride groups was determined to be 0.11 mmol / g and 2.81 mmol / g, respectively, as determined by titration following the procedure of Example 2. Example 33: Preparation poly [styrene-co-4-vinylbenzenesulfonic-co-vinylbenzylchloro-co-vinyl-2-pyridine-co-divinylbenzene]
[0295] The poly (styrene-co-vinylbenzylchloro-co-vinyl-2-pyridine-co-divinylbenzene) (5 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Cold concentrated sulfuric acid (> 98 w / w, H2 SO4 80 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a dark red paste. The slurry was stirred at 95 ° C for 8 h. After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum, washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The beads were finally sulfonated, washed with ethanol and air dried. The chemical functionalization of the polymer with sulfonic acid groups was determined to be 3.49 mmol / g, as determined by titration following the procedure of Example 2. Example 34: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co- vinylbenzylchloro-co-1-methyl-2-vinyl-pyridinium-co-divinylbenzene]
[0296] Poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloro-co-vinyl-2-pyridine-codivinylbenzene] (4 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2), with stirring, to obtain uniform viscous paste. Iodomethane (1.9 ml) was then added gradually into the flask followed by the addition of potassium iodide (10 mg). The reaction mixture was stirred at 95 ° C for 24 h. After cooling to room temperature, the cooled reaction mixture was filtered through a sintered glass funnel, under vacuum and then washed several times with diluted HCl solution to ensure complete exchange of r with Cl ". The resin beads were finally washed with deionized water until the effluent is neutral, as determined by pH indicator paper and then air dried. Example 35: Preparation of poly [styrene-co-4-vinylbenzenesulfonic-co- 4- ( 4-vinylbenzyl) -morpholine-oxide-4-co-divinylbenzene]
[0297] Poly [styrene-co-4- (4-vinylbenzyl) -morpholine-4-oxido-co-divinyl-benzene] (3 g) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser . Cold concentrated sulfuric acid (> 98 w / w, H2SO4 45 mL) was gradually added to the flask under agitation, therefore, which resulted in the formation of a dark red paste. The slurry was stirred at 95 ° C for 8 h. After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum, repeatedly washed with deionized water until the effluent was neutral, as determined by pH paper. The beads were finally sulfonated, washed with ethanol and air dried. Example 36: Preparation of poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]
[0298] Poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-iumchloro-co-divinylbenzene] (IC "density = ~ 2.73 mmol / g, 5 g) was loaded into a 100 ml flask equipped with a magnetic stir bar and condenser, diethylphosphite (30 ml) and t-butylperoxide (3.2 ml) were added to the flask and the resulting suspension was stirred at 120 ° C for 2 The reaction mixture was filtered using a glass frit funnel and the resin beads were washed several times with deionized water and ethanol These resin beads were then suspended in concentrated HCl (80 ml) and refluxed at 115 °. C, under continuous stirring, for 2 days After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water.The resin beads were finally washed with ethanol and air dried. The chemical functionalization of the polymer with an aromatic phosphonic acid group was terminated to be 0.15 mmol / g, as determined by titration following the procedure of Example 2. Example 37: Preparation of poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1- chloride-co-divinylbenzene]
[0299] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl "= density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dimethylformamide (50 ml) was added to the flask and stirred to form a resin slurry. Imidazole (2.8 g, 41.13mmol) was then added to the resin slurry and stirred at 80 ° C The reaction mixture was then cooled to 40 ° C and potassium i-butoxide (1.8 g) was added to the reaction mixture and stirred for 1 h. Bromoethylacetate (4 ml) was then added to the reaction mixture. mixture and the reaction was stirred at 80 ° C for 6 h After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water. washed and suspended in ethanolic sodium hydroxide solution and refluxed overnight.The resin granules were filtered and washed successively with deionized water multiple times and ethanol, and finally air dried. The chemical functionalization of the polymer with the carboxylic acid group was determined to be 0.09 mmol / g, as determined by titration following the procedure of Example 38: Preparation of lactic-co-isophthalic poly [styrene-5- (4-vinylbenzylamino) -3-methyl-l- (4-vinylbenzyl) -3H-imidazole-1-chloro-co-divinylbenzene]
[0300] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl “= density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser. Dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2) while stirring and, consequently, the uniform viscous paste of the polymer resin was obtained. Dimethyl aminoisoftalate (3.0 g, 14.3 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 16 h. 1-methylimidazole (2.3 mL, 28.4 mmol) was then added to the reaction mixture and stirred at 95 ° C for 1 day. After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol. The resin beads were washed and suspended in ethanolic sodium hydroxide solution and refluxed overnight. The resin beads were filtered and washed successively with deionized water and ethanol several times and, finally, air dried. The chemical functionalization of the polymer with the carboxylic acid group was determined to be 0.16 mmol / g, as determined by titration following the procedure of Example 2. Example 39: Preparation of poly [styrene-CO- (4-vinylbenzylamino) - acid acetic -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloro-co-divinylbenzene]
[0301] The poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (Cl "= density of ~ 4.0 mmol / g, 10 g, 40 mmol) was loaded into a 100 mL flask equipped with a stir bar magnetic and condenser, dry dimethylformamide (80 ml) was added to the flask (via a cannula under N2), while stirring and, consequently, the uniform viscous paste of the polymer resin was obtained. Glycine (1.2 g, 15, 9 mmol) was then added to the resin slurry and the resulting reaction mixture was stirred at 95 ° C for 2 days.1-methylimidazole (2.3 mL, 28.4 mmol) was then added to the reaction mixture and stirred. still at 95 ° C for 12 hours After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with deionized water and ethanol, and finally air dried. The chemical functionalization of the polymer with the carboxylic acid group was determined to be 0.05 mmol / g, as determined by tit using the procedure of Example 40: Preparation of poly [styrene-co (1-vinyl-1H-imidazole) -co-divinylbenzene]
[0302] To a 500 ml round-bottom flask (RBF) containing a stirred solution of 1.00 g of poly (vinyl alcohol) in 250, 0 ml of deionized H2O at 0 0 C is added gradually a solution containing 35 g (371mmol) of 1 - vinylimidazole, 10 g (96 mmol) of styrene, 1 g (7.7 mmol) of divinylbenzene (DVB) and 1.5 g (9.1 mmol) of azobisisobutyronitrile (AIBN) in 150 mL of a 1: 1 (by volume) benzene / tetrahydrofuran (THF) mixture at 0 ° C. After 2 hours of stirring at 0 ° C to homogenize the mixture, the reaction flask is transferred to an oil bath to increase the reaction temperature at 75 ° C, and the mixture is stirred vigorously for 24 hours. The resulting polymer is vacuum filtered using a glass frit funnel, washed several times with 20% (by volume) methanol in water, THF and MeOH, and then dried overnight at 50 ° C under reduced pressure. . Example 41: Preparation of poly (styrene-co-chloride of vinylbenzylmethylimidazolio-co-chloride-co vinylbenzylmethylmorpholinium-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)
[0303] 1-methylimidazole (4.61 g, 56.2 mmol), 4-methylmorpholine (5.65 g, 56.2 mmol), and triphenylphosphine (14.65, 55.9 mmol) were loaded in a flask 500 ml equipped with a magnetic stir bar and a condenser. Acetone (100 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (1% DVB, Cl- = density of 4.18 mmol / g dry resin, 40.22g, 168 mmol) was loaded into the flask with stirring until a uniform polymer suspension. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried overnight at 70 ° C. The chemical functionalization of the polymer resin with chloride of groups was determined to be 2.61 mmol / g of dry resin by means of titration. Example 42: Preparation of poly sulphonates (styrene-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co divinylbenzene)
[0304] The poly (styrene-co-chloride-co vinylbenzylmethylimidazolium vinylbenzylmethylmorpholinium chloride-co-chloride vinylbenzyltriphenylphosphonium codivinylbenzene) (35.02 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 175 mL) was gradually added to the flask and stirred to form the dark red resin suspension. The mixture was stirred overnight at 90 ° C. After cooling to room temperature, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated polymer resin was air-dried to a final moisture content of 56% g H2O / g wet polymer. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.65 mmol / g of dry resin. Example 43: Preparation of poly (styrene-co-chloride of vinylbenzylmethylimidazolio-co-chloride-co vinylbenzylmethylmorpholinium -vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene)
[0305] 1-methylimidazole (7.02 g, 85.5 mmol), 4-methylmorpholine (4.37 g, 43.2 mmol) and triphenylphosphine (11.09, 42.3 mmol) were loaded into a flask. 500 ml equipped with a magnetic stir bar and condenser. Acetone (100 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (1% DVB, Cl- = density of 4.18 mmol / g dry resin, 40.38g, 169 mmol) was loaded into a stirred flask until a suspension was obtained uniform. The resulting reaction mixture was refluxed for 18 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. The chemical functionalization of the polymer resin with chloride groups was determined to be 2.36 mmol / g of dry resin from dry resin by means of titration. Example 44: Preparation of poly sulphonates (styrene-co-vinylbenzylmethylimidazole bisulfate-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co divinylbenzene)
[0306] Poly (styrene-co-vinylbenzylmethylimidazolium -co - vinyl-benzylmethylmorpholinium chloride -co-vinylbenzyltriphenylphosphonium co-divinylbenzene) (35.12 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 175 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The beads were finally sulfonated and air dried. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.38 mmol / g of dry resin. Example 45: Preparation of poly (styrene-vinylbenzylmethylmorpholine-co-chloride, vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0307] 4-methylmorpholine (8.65 g, 85.5 mmol) and triphenylphosphine (22.41, 85.3 mmol) were loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Acetone (100 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene vinylbenzylchloro-co-divinylbenzene) (1% DVB, Cl- = density of 4.18 mmol / g of dry resin, 40.12 g, 167 mmol) were loaded into a flask with stirring until a suspension was obtained homogeneous was obtained. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. The chemical functionalization of the polymer resin with chloride groups was determined to be 2.22 mmol / g dry resin via titrimetry. Example 46: Preparation of polysulfonates (styrene-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene)
[0308] The poly (styrene-co-vinylbenzylmethylimidazolium -co - vinyl-benzylmethylmorpholinium -co-chloride vinylbenzyltriphenylphosphonium co-divinylbenzene) (35.08 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 175 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulphonated and dried in air to a final moisture content of 52% g H2O / g wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.24 mmol / g of dry resin. Example 47: Preparation of phenol-formaldehyde resin
[0309] phenol (12.87 g, 136.8 mmol) was dispensed into a 100 ml round bottom flask (BFR) equipped with a stir bar and condenser. Deionized water (10g) was loaded into the flask. 37% formalin solution (9.24 g, 110 mmol) and oxalic acid (75 mg) were added. The resulting reaction mixture was refluxed for 30 min. Additional oxalic acid (75mg) was then added and reflux continued for an additional 1 hour. A piece of solid resin was formed, which was ground to a coarse powder using a mortar and pestle. The resin was washed several times with water and methanol and then dried at 70 ° C overnight. Example 48: Preparation of chloromethylated phenol-formaldehyde resin
[0310] Phenol-formaldehyde resin (5.23 g, 44 mmol) was distributed in a 100-ml three-necked round-bottom (BFR) flask equipped with a stir bar, condenser and nitrogen atmosphere line. Anhydrous dichloroethane (DCE, 20 ml) was then loaded into the flask. For ice chilled resin suspension in DCE, zinc chloride (6.83 g, 50 mmol) was added. Chloromethyl methyl ether (4.0 ml, 51 mmol) was then added dropwise to the reaction. The mixture was warmed to room temperature and stirred at 50 ° C for 6 h. The product resin was recovered by vacuum filtration and was washed sequentially at 40 ° C overnight. Example 49; Preparation of functionalized phenol-formaldehyde triphenylphosphine resin
[0311] triphenylphosphine (10.12, 38.61 mmol) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Acetone (30 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Chloromethylated phenol-formaldehyde resin (4.61g, 38.03 mmol) was loaded into a shaking flask. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. Example 50: Preparation of sulfonated phenol-formaldehyde resin functionalized with triphenylphosphine
[0312] Phenol-formaldehyde resin functionalized with triphenylphosphine (5.12 g, 13.4 mmol) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 25 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin was dried in air with a final moisture content of 49% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.85 mmol / g of dry resin. Example 51: Preparation of poly (styrene-co-vinylimidazole-co-divinylbenzene)
[0313] Deionized water (75 mL) was loaded into a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, condenser and N2. Sodium chloride (1.18 g) and carboxymethylcellulose (0.6 lg) were loaded into the flask and stirred for 5 min. The solution of vinylimidazole (3.9 mL, 42.62 mmol), styrene (4.9 mL, 42.33 mmol) and divinylbenzene (0.9 mL, 4.0 mmol) in isooctanol (25 mL) was loaded into the balloon. The resulting emulsion was stirred at 500 rpm at room temperature for 1 h. Benzoyl peroxide (75%, 1.205 g) was added, and the temperature was increased to 80 ° C. The reaction mixture was heated for 8 h at 80 ° C with a stirring speed of 500 rpm. The polymer product was recovered by vacuum filtration and washed with water and acetone several times. The isolated polymer was purified by extracting Soxhlet with water and acetone. The resin was dried at 40 ° C overnight. Example 52: Preparation of poly (styrene-co-vinylmethylimidazolium iodide-co-divinylbenzene)
[0314] The poly (styrene-co-vinylimidazole-co-divinylbenzene) (3.49 g, 39 mmol) was distributed in a 100 ml three-necked round neck (BFR) flask equipped with a stir bar line , condenser and nitrogen atmosphere. Anhydrous tetrahydrofuran (20 ml) was then loaded into the flask. For ice-cooled resin suspension in tetrahydrofuran, potassium t-butoxide (5.62 g, 50 mmol) was added and stirred for 30 min. iodomethane (3.2 ml, 51 mmol) was then added dropwise to the reaction. The mixture was warmed to room temperature and stirred at 50 ° C for 6 h. The product resin was recovered by vacuum filtration and washed sequentially with water, acetone and dichloromethane. The washed resin was dried at 40 ° C overnight. Example 53: Preparation of poly sulfonates (styrene-co-vinylmethylimidazolium bisulfate-co-divinylbenzene)
[0315] The poly (styrene-co-vinylmethylimidazolium iodide-codivinylbenzene) (3.89 g, 27.8 mmol) was loaded into a 100 mL flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 20 mL) was gradually added to the flask and stirred to form a dark red paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The sulfonated polymer was dried in air with a final moisture content of 51% g H2O / g of wet resin. Example 54: Preparation of poly (styrene-vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0316] Triphenylphosphine was loaded into a 250 ml flask equipped with a magnetic stir bar and a condenser was loaded (38.44 g, 145.1mmol). Acetone (50 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (8% DVB, Cl "= density of 4.0 mmol / g dry resin, 30.12 g, 115.6 mmol) was loaded into a flask with stirring until The resulting reaction mixture was heated to reflux for 24 h. After cooling, the reaction mixture was filtered through a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried. at 70 ° C overnight The chemical functionalization of the polymer resin with triphenylphosphonium groups was determined to be 1.94 mmol / g of dry resin by means of titration Example 55: Preparation of poly sulphonates (styrene-co-vinylbenzyltriphenyl) phosphonium bisulfate-co-divinylbenzene)
[0317] The poly (styrene-CO-vinylbenzyltriphenylphosphonium chloride-codivinylbenzene) (40.12 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 160 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air to a final moisture content of 54% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.39 mmol / g of dry resin. Example 56: Preparation of poly (styrene-vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0318] Triphenylphosphine was loaded into a 250 ml flask equipped with a magnetic stir bar and a condenser was loaded (50.22 g, 189.6 mmol). Acetone (50 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (4% DVB, Cl "= density of 5.2 mmol / g dry resin, 30.06 g, 152.08 mmol) was loaded into a flask with stirring until a uniform suspension was obtained The resulting reaction mixture was refluxed for 24 h After cooling, the reaction mixture was filtered using vacuum frit funnel, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight The chemical functionalization of the polymer resin with triphenylphosphonium groups was determined to be 2.00 mmol / g dry resin via titrimetry Example 57: Preparation of poly sulphonates (styrene-co-vinylbenzyltriphenyl) phosphonium bisulfate-co-divinylbenzene)
[0319] The poly (styrene-co-vinylbenzyltriphenylphosphonium-co-divinylbenzene) (40.04 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 160 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air to a final moisture content of 47% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.36 mmol / g of dry resin. Example 58: Preparation of poly (styrene-vinylbenzylmethylimidazolium-co-divinylbenzene)
[0320] Magnetic 1-methylimidazole (18 mL, 223.5 mmol) was loaded into a 250 ml flask equipped with a stir bar and condenser. Acetone (75 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (8% DVB, Cl “= density of 4.0 mmol / g dry resin, 40.06, 153.7 mmol) was loaded into a flask with stirring until obtain a homogeneous suspension. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. The chemical functionalization of the polymer resin with methylimidazolium chloride groups was determined to be 3.54 mmol / g of dry resin by means of titration. Example 59: Preparation of polysulfonates (styrene-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene)
[0321] The poly (styrene-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene) (30.08 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 120 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air until a final moisture content of 50% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.87 mmol / g of dry resin. Example 60: Preparation of poly (styrene-co-vinylbenzylmethylimidazolium-co-divinylbenzene)
[0322] Magnetic 1-methylimidazole (20 mL, 248.4 mmol) was loaded into a 250 ml flask equipped with a stir bar and condenser. Acetone (75 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (4% DVB, Cl "= density of 5.2 mmol / g dry resin, 40.08, 203.8 mmol) was loaded into a flask with stirring until obtaining a homogeneous suspension was obtained.The resulting reaction mixture was refluxed for 24 h After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight The chemical functionalization of the polymer resin with methylimidazolium chloride groups was determined to be 3.39 mmol / g of dry resin by means of titration Example 61: Preparation of poly sulphonates (styrene- co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene)
[0323] The poly (styrene-CO-vinylbenzylmethylimidazolium chloride-codivinylbenzene) (30.14 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 120 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air to a final moisture content of 55% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.78 mmol / g of dry resin. vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0324] Triphenylphosphine was loaded into a 250 ml flask equipped with a magnetic stir bar and a condenser was loaded (44.32 g, 163.9mmol). Acetone (50 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (13% macroporous resin DVB, Cl- = density of 4.14 mmol / g dry resin, 30.12 g, 115.6 mmol) was loaded into a shaking flask until you get a uniform suspension. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. Example 63; Preparation of poly sulphonates (styrene-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene)
[0325] The poly (styrene-CO-vinylbenzyltriphenylphosphonium chloride-codivinylbenzene) (30.22 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 90 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C for 1 hour. After cooling, the reaction mixture was then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air to a final moisture content of 46% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.82 mmol / g of dry resin. Example 64: Preparation of poly (styrene-vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0326] Triphenylphosphine was loaded into a 250 ml flask equipped with a magnetic stir bar and a condenser was loaded (55.02 g, 207.7mmol). Acetone (50 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (6.5% DVB macroporous resin, Cl "= density of 5.30 mmol / g dry resin, 30.12 g, 157.4 mmol) was loaded into a vial with stirring until a uniform suspension is obtained The resulting reaction mixture was refluxed for 24 h After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight Example 65: Preparation of poly sulphonates (styrene-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene)
[0327] The poly (styrene-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) (30.12 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 90 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C for 1 hour. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed repeatedly with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air to a final moisture content of 49% g H 2 0 / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.82 mmol / g of dry resin. Example 66: Preparation of poly (styrene-vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0328] Triphenylphosphine was loaded into a 250 ml flask equipped with a magnetic stir bar and a condenser was loaded (38.42 g, 145.0 mmol). Acetone (50 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (4% DVB, Cl- = density of 4.10 mmol / g dry resin, 30.12 g, 115.4 mmol) was loaded into a flask with stirring until get a uniform suspension. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. Example 67: Preparation of poly sulphonates (styrene-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene)
[0329] The poly (styrene-CO-vinylbenzyltriphenylphosphonium chloride-codivinylbenzene) (30.18 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 120 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum and then washed several times with deionized water until the effluent was neutral, as determined by pH paper. The granules were sulfonated and dried in air to a final moisture content of 59% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.03 mmol / g of dry resin. vinylbenzyltriphenylphosphonium-co-divinylbenzene)
[0330] Triphenylphosphine was loaded into a 500 ml flask equipped with a magnetic stir bar and a condenser was loaded (44.22 g, 166.9 mmol). Acetone (70 ml) was added to the flask and the mixture was stirred at 50 ° C for 10 min. Poly (styrene-co-vinylbenzylchloro-co-divinylbenzene) (4% DVB, Cl- = density of 3.9 mmol / g dry resin, 35.08 g, 130.4 mmol) was loaded into a flask with stirring until a uniform suspension was obtained. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a glass frit funnel under vacuum, washed sequentially with ethyl acetate and acetone, and dried at 70 ° C overnight. Example 69: Preparation of poly sulfonates (styrene-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene)
[0331] The poly (styrene-co-vinylbenzyltriphenylphosphonium chlorocodivinylbenzene) (30.42 g) was loaded into a 500 ml flask equipped with a magnetic stir bar and condenser. Smoking sulfuric acid (20% free SO3, 120 mL) was gradually added to the flask and stirred to form a dark red resin paste. The slurry was stirred at 90 ° C overnight. After cooling, the vacuum mixture is then washed several times with deionized water until the effluent is neutral, as determined by pH paper. The granules were sulphonated and dried in air to a final moisture content of 57% g H2O / g of wet resin. The chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.04 mmol / g of dry resin. Example 70: Preparation of poly (butyl vinyl imidazolium-co-butylimidazolium-co-styrene chloride)
[0332] To a 500 ml flask equipped with a mechanical stirrer and reflux condenser, 250 ml of acetone, 10 g of imidzole, 14 g of vinylimidazole, 15 g of styrene, 30 g of dichlorobutane and 1 g of azobisisobutyronitrile (AIBN) are added. The solution is stirred under reflux conditions for 12 hours to produce a solid polymer mass. The solid polymer is removed from the flask, washed repeatedly with acetone, and ground to a coarse powder using a mortar and pestle to obtain the product. Example 71: Preparation of poly sulphonates (butyl vinyl imidazole bisulfate-co-butyl imidazole bisulfate-co-styrene)
[0333] Poly (butyl vinylimidazolium chloride-butylimidazolium-co-styrene), 30.42 g) is loaded into a 500 ml flask equipped with a mechanical stirrer. Smoking sulfuric acid (20% free SO3, 120 ml) is added gradually into the bottle until the polymer is fully suspended. The resulting slurry is stirred at 90 ° C for 5 hours. After cooling, the reaction mixture is filtered through a glass frit funnel under vacuum and then washed several times with deionized water until the effluent is neutral, as determined by pH paper. Catalytic digestion of lignocellulosic materials Example Bl: Digestion of sugarcane bagasse using the catalyst described in Example 3
[0334] Sugar cane bagasse (50% g H2O / g wet bagasse, with a dry matter composition of: 39.0% g glucan / g dry biomass, 17.3% g xylan / g of dry biomass, 5.0% g arabinan / g of dry biomass, 1.1% g galactan / g of dry biomass, 5.5% g of ethyl / g of dry biomass, 5.0% g of extracts / g of soluble dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g ash / g dry biomass) was cut, so that the maximum particle size was not greater than 1 cm . The composition of lignocellulosic biomass was determined using a method based on procedures known in the art. See R. Ruiz and T. Ehrman, "determination of carbohydrates in biomass by High Performance Liquid Chromatography", NREL Laboratory analytical procedure LAP-002 (1996); D. Tempelton and T. Ehrman, "Determination of acid and lignin insoluble in Biomass," NREL Laboratory analytical procedure LAP-003 (1995); T. Erhman, "Determination of Acid-Soluble Lignin in Biomass," NREL Laboratory analytical procedure LAP-004 (1996); and T. Ehrman, "Standard Method for Ash in Biomass," NREL Laboratory analytical procedure LAP-005 (1994).
[0335] To a glass reaction bottle, a 15 ml cylindrical one was added: 0.50 g of the sugarcane bagasse sample, 0.30 g of catalyst prepared as in Example 3 (the initial content of humidity: 12% g H2O / g catalyst dispensed), and 800 pl H2O deionized. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 120 ° C for four hours. Example B2: Separation of Catalyst / Product Mixture from the hydrolysis of sugarcane bagasse
[0336] The cylindrical glass reactor of Example 41 was cooled to room temperature and unsealed. 5.0 mL of distilled H2O was added to the flask reactor and the resulting mixture of liquid and solid products was stirred for 2 minutes by magnetic stirring. After stirring, the solids were allowed to settle for 30 seconds to produce the layered mixture. The solid catalyst formed a layer at the bottom of the flask reactor. Lignin and residual biomass are formed in the solid layer above the solid catalyst. Short-chain beta-glucans formed a layer of amorphous solids above lignin and residual biomass. Finally, the soluble sugars formed a liquid layer above short-chain beta-glucans. Example B3: Recovery of sugars and soluble carbohydrates from the hydrolysis of sugarcane bagasse
[0337] The supernatant and residual insoluble materials from Example 42 were separated by decantation. The content of soluble sugar in hydrolysis products was determined by a combination of high performance liquid chromatography (HPLC) and spectrophotometric methods. HPLC determination of soluble sugars and oligosaccharides was performed on a Hewlett-Packard Series 1050 instrument equipped with a refractive index (IR) detector using a 30 cm x 7.8 mm Phenomenex HPB Column with water as the mobile phase . The sugar column was protected both by a sulfonated-lead-exchange polystyrene guard column and a trialkylammonium hydroxide exchange anion guard column. All HPLC samples were microfiltered using a 0.2 pm syringe filter prior to injection. Sample concentrations were determined by reference to a calibration generated from known standards.
[0338] The ability of the catalyst to hydrolyze the cellulose and hemicellulose components of biomass into soluble sugars was measured by determining the effective rate constant of the first order. The extent of the reaction of a chemical species (eg, glucan, xylan, arabinan) was determined by calculating the ratio of moles of isolated species to the theoretical moles of the species that would be obtained as a result of complete conversion of the input reagent based on the known composition of the incoming biomass and the known molecular weights of the reagents and products and the known stoichiometries of the reactions under consideration.
[0339] For the digestion of sugarcane bagasse using a catalyst, as described in Example 3, the first order rate constant for the conversion of xylan to xylose was determined to be 0.3 / hour. The first order rate for the constant conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.08 / hr. Example B4: Recovery of insoluble oligo-glucans from sugarcane bagasse hydrolyzate
[0340] An additional 5.0 ml of water was added to the residual solids from Example 43 and the mixture was stirred gently to suspend only the lightest particles. The suspension was decanted to remove light particles from the residual lignin and residual catalyst, which remained in the solid sediment at the bottom of the reactor. The solid particles were concentrated by centrifugation.
[0341] The average number of degree of polymerization (DOPN) of residual water insoluble glucans (including short chain oligosaccharides) was determined by extracting the glucans in cold phosphoric acid, precipitating the extracted carbohydrates in water, and measuring the terminal ratio of reducing sugars to the number of total sugar monomers by the method of Zhang and Lynd. See Y.-H. Percival Zhang and Lee R. Lynd, "Determination of the Umber average degree of polymerization of Cellodextrins and Cellulose with application for enzymatic hydrolysis", Biomacromolecules, 6, 1510 - 1515 (2005). UV-Visible spectrophotometric analysis was performed on a Beckman DU-640 instrument. In cases where hemicellulose digestion was complete (as determined by HPLC), extraction with phosphoric acid is required. In some cases, the number of average degree of polymerization was verified by means of Cell Permeation Gel Chromatography (GPC) performed using a procedure adapted from the method of Evans et al. See R. Evans, R. Wearne, AFA Wallis, "Molecular weight distribution of cellulose as its High Performance Size Exclusion Chromatography", J. Appl. Pol. Set, 37, 3291-3303 (1989).
[0342] In a 20 ml reaction flask containing 3 ml of dry DMSO, a sample of about 50 mg of cellulose was suspended (dried overnight at 50 ° C under reduced pressure). The reaction flask was sealed with a PTFE septum, washed with dry N2, followed by the addition of 1.0 ml of phenyl isocyanate via a syringe. The reaction mixture was incubated at 60 ° C for 4 hours with periodic mixing, until most of the cellulose has dissolved. The excess of isocyanate was extinguished by the addition of 1.0 mL of dry MeOH. Residual solids were pelleted by centrifugation, and a 1 ml aliquot of the supernatant was added to 5 ml of 30% v / v MeOH / dfoO to produce the carbanylated cellulose as a white precipitate. The product was recovered by centrifugation, and washed repeatedly with 30% v / v MeOH, followed by drying for 10 hours at 50 ° C under reduced pressure. GPC was performed on a Hewlett-Packard 1050 Series HPLC using a series of columns and tetrahydrofuran (THF) as the mobile phase with TSK-Gel / Vis UV detection (G3000Hhr, G4000Hhr, G5000Hhr). The molecular weight distribution of cellulose was determined using a calibration based on known molecular weight standards of polystyrene.
[0343] For the digestion of sugarcane bagasse using a catalyst, as shown in Example 3, the number of average degree of polymerization of the oligoglucans was determined to be 19 ± 4 units of anhydroglucose (AHG). The observed reduction in the degree of polymerization of the residual cellulose to a value significantly less than the degree of polymerization for the crystalline domains of the incoming cellulose (for which PDO N> 200 AHG units) indicates that the successfully hydrolyzed catalyst of crystalline cellulose . The first order constant for the conversion of short-chain β-glucan to oligo-glucans was determined to be 0.2 / h. Example B5: Lignin Separation and Recovery, which did not react with Biomass and Residual and Hydrolyzed Sugarcane Bagasse Catalyst
[0344] An additional 10 ml of water was added to the residual solids in Example 44. The mixture was stirred to suspend the residual lignin (and residual unreacted biomass particles) without suspending the catalyst. The recovered catalyst was washed with water and then dried to constant mass at 110 ° C in a gravity oven to obtain 99.6% g / g of recovery. The functional density of sulfonic acid groups on the recovered catalyst was determined to be 1.59 ± 0.02 mmol / g by titration of the recovered catalyst indicating a negligible loss of acid functionalization. Example B6: Reuse of Recovered Catalyst
[0345] Some of the catalysts recovered from Example 45 (0.250 g dry base) were returned to the 15 ml bottle of the cylindrical reactor. 0.50 g of additional biomass (identical composition to that of Example 45) and 800 of deionized H2O was added to the reactor and the contents were mixed carefully, as described in Example 41. The reactor was sealed and incubated at 115 ° C for four hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The first order rate constant for the conversion of xylan to xylose was determined to be 0.3 / hour. The first order rate for the constant conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.1 / h. The number of average degree of polymerization of the residual cellulose was determined to be DOPN = 20 ± 4AHG units, and the first order constant for the conversion of short-chain β-glucan to oligo-glucans was determined to be 0.2 / H. Example B7: Corn Stover Hydrolysis using Catalyst prepared as in Example 34
[0346] Corn straw (7.2% g H2O / g wet biomass, with a dry matter composition: 33.9% g glucan- / g dry biomass, 24.1% g xylan / g dry biomass , 4.8% g arabinan / g dry biomass, 1.5% g galactan / g dry biomass, 4.0% g ethyl / g dry biomass, 16.0% g extractives / g dry biomass soluble, 11.4% g lignin / g dry biomass, and 1.4% g gray / g dry biomass) were cut, so that the maximum particle size was not greater than 1 cm. For a 15 ml vial of cylindrical glass reaction, 0.45 g of the sugarcane bagasse sample, 0.22 g of catalyst prepared as in Example 34 (initial moisture content: 0.8% g of H2O / g of catalyst dispensed), and 2.3 ml of ionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 110 ° C for five hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The first order rate of the constant for converting xylan to xylose was determined to be 0.1 / h. The first order rate for the constant conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.04 / hr. The number of average degree of polymerization of the residual cellulose was determined to be DOP N = 20 ± 4 AHG units, and the first order constant for the conversion of short-chain β-glucan to oligo-glucans was determined to be 0.06 / hr. Example B8: Hydrolysis of empty palm oil clusters using the catalyst prepared as in Example 20
[0347] Palm oil from empty cluster fruits (8.7% g H2O / g wet biomass, with a dry matter composition: 35.0% g glucan / g dry biomass, 21.8% g xylan / g dry biomass, 1.8% arabinan / g dry biomass, 4.8% ethyl / g dry biomass, 9.4% extractive g / g soluble dry biomass, 24.2% g lignin / g of dry biomass, and 1.2% of ash / g of dry biomass) was cut so that the maximum particle size was not greater than 1 cm. To a 15 ml flask of cylindrical glass reaction was added: 0.46 g of the sugarcane bagasse sample, 0.43 g of catalyst prepared as in Example 20 (initial moisture content: 18.3% g H2O / g of catalyst dispensed), and 1.3 ml of ionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 110 ° C for five hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The constant first order rate for converting xylan to xylose was determined to be 0.4 / h. The first order rate for the constant conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.04 / hr. The number of average degree of polymerization of residual cellulose was determined to be DOPN = 20 ± 4AHG units, and the first order constant for the conversion of short-chain β-glucan to oligo-glucans was determined to be 0.06 / hr . Example B9: Hydrolysis of sugarcane bagasse using catalyst prepared as in Example 32
[0348] Sugar cane bagasse (12.5% g H2O / g wet bagasse, with a dry matter composition: 39.0% g glucan / g dry biomass, 17.3% g xylan / g dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extracts / g of dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g ash / g dry biomass) was cut, in such a way that the maximum particle size was not greater than 1 cm. To a 15 ml vial of cylindrical glass reaction was added: 0.53 g of the sugarcane bagasse sample, 0.52 g of catalyst prepared as in Example 32 (initial moisture content: 3.29% g H2O / g catalyst dispensed), and 1.4 mL of deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for four hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The constant first order rate for converting xylan to xylose was determined to be 0.59 / hr. The first order rate for the constant conversion of soluble glucan monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.05 / hr. The average number of degree of polymerization of the residual cellulose was determined to be DOPN = 23 + 4AHG units, and the first order rate constant for the conversion of short-chain β-glucan to oligoglucans was determined to be 0.07 / hr. Example B10: Hydrolysis of sugarcane bagasse using catalyst prepared as in Example 18.
[0349] Sugarcane bagasse (12.5% g H2O / g wet bagasse, with a dry matter composition: 39.0% g sugar glucan / g dry biomass, 17.3% g xylan / g dry biomass, 5.0% arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extracts / g dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g gray / dry biomass) was cut, so that the maximum particle size was not greater than than 1 cm. To a 15 ml vial of cylindrical glass reaction, 0.51 g of sugarcane bagasse sample, 0.51 g of catalyst prepared as in Example 18 (initial moisture content: 7.9% g H 2 O / g of catalyst dispensed) and 1.4 ml of deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for four hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The constant first order rate for conversion from xylan to xylose was determined to be 0.06 / hr. The first order rate for the constant conversion of soluble glucan to oligo-, di-, and monosaccharides was determined to be 0.05 / hr. The number of average degree of polymerization of the residual cellulose was determined to be 20 ± 4AHG units, and the first order constant for the conversion of short-chain β-glucan to oligo-glucans was determined to be 0.07 / hr. Example Bll: High selectivity for sugars
[0350] Chopped palm oil from bunches of empty fruit (8.7% g H2O / g wet biomass, with a dry matter composition: 35.0% g glucan / g dry biomass, 21.8% g xylan / g of dry biomass, 1.8% g arabinan / g of dry biomass, 4.8% g of acetate / g of dry biomass, 9.4% g soluble extracts / g of dry biomass, 24.2% g lignin / g of dry biomass, and 1.2% ash g / g of dry biomass) was cut, so that the maximum particle size other than cylindrical glass was added 0.51 g of sugarcane bagasse sample, 0.51 g of catalyst prepared as in Example 3 (initial moisture content: 8.9% g of H2O / g of catalyst dispensed), and 2.6 ml of deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for four hours. Following the reaction, 10.0 ml of deionized H2O was added to the mixture to dissolve the product into the soluble species and the solids were left to sediment. HPLC determination of sugar dehydration products and organic acids released from biomass samples was performed on an Agilent 1100 Series instrument using a 7.8mm x Supelcogel ™ H 30cm column (or a Phenomenex HOA Column in some cases ) with 0.005N sulfuric acid in water as a mobile phase. The quantification of sugar degradation products: formic acid, levulinic acid, 5-hydroxymethylfurfural and 2-furaldehyde was performed by reference to a calibration curve produced from solutions of high purity of known concentration. The first order velocity constant for the production of degradation products was found to be <0.001 / hr, which represents> 99% mol of sugars / mol of degradation products. Example B12: Fermentation of cellulosic sugars from sugarcane bagasse
[0351] Sugarcane Bagasse (12.5% G H2o / G Wet Bagasse, With a Dry Matter Composition: 39.0% G Sugar Glucane / G Dry Biomass, 17.3% G Xylan / G Dry Biomass, 5.0% G Arabinane / G Dry Biomass, 1.1% G Galactane / G Dry Biomass, 5.5% G Acetate / G Dry Biomass, 5.0% G Extracts Soluble / G Dry Biomass, 24.1% G Lignin / G Dry Biomass, And 3.1% G Ash / G Dry Biomass) was cut so that the maximum particle size was not greater than That 1 Cm. A 15 Ml Cylindrical Glass Reaction Vial was added: 1.6 G Sample, Sugarcane Bagasse, 1.8 G Catalyst Prepared as in Example 3 (Initial Moisture Content: 12.1 % G H2o / G Catalyst Dispensed), and 5.0 Ml Ionized H2o. The Reagents were carefully mixed with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 110 ° C for five hours. After five hours, an additional 1.0 ml of distilled H2O was added to the reaction mixture, which was then incubated at 105 ° C for an additional 2 hours. The wet reagent cake was loaded into a syringe equipped with a 0.2 micrometer filter and the hydrolyzate was pressed out of the product mixture into a sterile container. A culture tube was added to 2.5 ml of culture medium (prepared by diluting 10 g of yeast extract and 20 g of peptone to 500 ml of distilled water, followed by purification by means of sterile filtration), 2, 5 Ml Of Hydrolyzate, And 100 Ml Of Yeast Paste (Prepared By Dissolving 500 Mg Of 24 Hours Alcotec Turbo Super Yeast In 5 Ml Of 30 ° C Sterile H2o. The Culture Was Grown At 30 0 C In The Shaking Incubator, With 1 Ml aliquots removed at 24, 48 and 72 hours.For each aliquot, the optical density of the culture was determined by an aliquot in a spectrophotometer.The aliquot was purified by centrifugation and the supernatant was analyzed by Hplc to determine glucose concentrations Xylose, Galactose, Arabinose, Ethanol And Glycerol After 24 hours, ethanol and glycerol were found in the fermentation supernatant, indicating at least 65% of fermentation yield on a molar basis in relation to the initial glucose in the hydrolyzate. Example B13 : Fermentation Of Cellulosic Sugar From Cassava Stem
[0352] Cassava stem (2.0% g H2O / g wet cassava stem, with a dry matter composition: 53.0% sugar glucan / g dry biomass, 6.0% x xylan / g of dry biomass, 2.5% g arabinane / g dry biomass, 5.5% g ethyl / g dry biomass, 5.9% g soluble extracts / g soluble dry biomass, 24.2% g lignin / g of dry biomass, and 2.1% g ash / g of dry biomass) was cut in a coffee grinder, in such a way that the maximum particle size was not more than 2 mm. To a 15 ml vial of cylindrical glass reaction was added: 1.9 g of cut cassava stems, 2.0 g of catalyst prepared as in Example 3 (initial moisture content: 12.0% g H2O / g of catalyst dispensed), and 8.0 ml of deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 110 ° C for five hours. After five hours, an additional 2.0 mL of distilled H2O was added to the reaction mixture, which was then incubated at 105 ° C for an additional 2 hours. The wet reagent cake was loaded into a syringe equipped with a 0.2 micrometer filter and the hydrolyzate was pressed out of the product mixture into a sterile container. To a culture tube, 2.5 ml of culture medium was added (prepared by diluting 10 g of yeast extract and 20 g of peptone to 500 ml in distilled water, followed by purification by means of sterile filtration), 2, 5 ml of the hydrolyzate, and 100 ml of yeast paste (prepared by dissolving 500 mg of 24 hours Alcotec Turbo Super yeast in 5 ml of 30 0 C of sterile H2O. The culture was grown at 30 ° C in the shaking incubator, with 1 ml aliquots removed at 24, 48 and 72 hours For each aliquot, the optical density of the culture was determined by aliquot in a spectrophotometer. The aliquot was purified by centrifugation and the supernatant was analyzed by HPLC to determine glucose concentrations, xylose, galactose, arabinose, ethanol and glycerol After 24 hours, ethanol and glycerol were found in the fermentation in the supernatant, indicating at least 70% fermentation yield on a molar basis in relation to the initial glucose in the hydrolyzate. Example B14: Glucose fermentation obtained from insoluble starch
[0353] To a 15 mL cylindrical glass reaction flask was added: 4.0 g of corn starch (3 g% H 2 0 / g wet starch, with a dry matter composition: 98% glucan g / g of dry biomass), 3.9 g of catalyst prepared as in Example 3 (initial moisture content: 12.25% g H2O / g of catalyst dispensed), and 12.0 ml of deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 110 ° C for five hours. After five hours, an additional 2.0 mL of distilled H2O was added to the reaction mixture, which was then incubated at 105 ° C for an additional 2 hours. The wet reagent cake was loaded into a syringe equipped with a 0.2 micron filter and the hydrolyzate was pressed out of the product mixture into a sterile container. To a culture tube, 2.5 ml of culture medium was added (prepared by diluting 10 g of yeast extract and 20 g of peptone to 500 ml in distilled water, followed by purification by means of sterile filtration), 2, 5 ml of the hydrolyzate, and 100 ml of yeast paste (prepared by dissolving 500 mg of 24 hours Alcotec Turbo Super yeast O in 5 ml of 30 C of sterile H2O. The culture was grown at 30 ° C in the shaking incubator, with 1 ml aliquots removed at 24, 48 and 72 hours. For each aliquot, the optical density of the culture was determined by aliquot spectrophotometry. The aliquot was purified by centrifugation and the supernatant was analyzed by HPLC to determine glucose concentrations, xylose, galactose, arabinose, ethanol and glycerol.After 24 hours, ethanol and glycerol were found in the fermentation supernatant, indicating at least 88% fermentation yield on a molar basis compared to the initial glucose in the hydrolyzate. : Sa enzymatic charification of oligoglucans obtained from the digestion of sugarcane bagasse with the catalyst as prepared in Example 3
[0354] 50.0 mg of the oligogucans obtained in Example 44 were suspended in 0.4 ml of 0.05 molar acetate buffer solution at pH 4.8 in a culture tube. The suspension was preheated to 40 ° C, after which, 0.5 FPU of cellulase enzyme from Trichoderma reesei Celluclast® and 2 IU of cellulose enzyme from Aspergillus niger (diluted in 0.1 ml of citrate buffer at 40 ° C ) was added. A 50.0 mL aliquot was sampled from the hourly enzyme reaction for five hours. For each aliquot, the reaction was terminated by diluting the sample from 50.0 mL to 0.7 mL of distilled water and adding 0.3 mL of DNS reagent (prepared by diluting 91 g of sodium potassium tartrate, 3, 15 g dinitrosalicylic acid, 131 ml of 2 molar sodium hydroxide, 2.5 g of phenol and 2.5 g of sodium sulfite for 500 ml with H2O). The 1 ml mixture was sealed in a microcentrifuge tube and boiled for exactly 5 minutes in water. The appearance of reducing sugars was measured by comparing the absorbance at 540 nm with a calibration curve generated from glucose samples of known concentration. The first order velocity constant for reducing sugar release in the saccharification reaction was determined to be 0.15 / hr. Comparative Example B16: Attempt to hydrolysis of sugarcane bagasse with polystyrene-sulfonates, cross-linked (Negative Control 1)
[0355] The cellulose digestion capacity of the catalysts described here has been compared to that of conventional polymeric-acidified resins used for catalysis in organic and industrial chemistry (T. Okuhara, "Water-Tolerant solid acid catalysts," Chem. Rev. ., 102, 3641-3666 (2002)). Sugarcane bagasse (12.5% g H2O / g wet bagasse, with a dry matter composition: 39.0% g glucan / g dry biomass, 17.3% g xylan / g dry biomass, 5.0% arabinan g / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% soluble extracts / g dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g gray / g dry biomass) was cut, so that the maximum particle size was not greater than 1 cm. To a 15 ml glass cylindrical reaction flask, 0.51 g of the sugarcane bagasse sample, 0.53 g of sulfonated polystyrene (Dowex® 50WX2 resin, acid functionalization: 4.8 mmol / g, initial moisture content: 19.6% g H2O / g catalyst dispensed), and 1.4 mL deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for six hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The constant first order rate for conversion from xylan to xylose was determined to be 0.1 / h. The first order rate for the constant conversion of soluble glucan to oligo-, di-, and monosaccharides was determined to be <0.01 / hr. The number of average degree of polymerization of residual cellulose was found to be DOPN units> 300AHG, which indicates little or no digestion of crystalline cellulose in the biomass sample. Short chain oligosaccharides were not detected. Unlike the digestion products represented in Figure (1), the residual biomass exhibited little or no structural reduction in particle size. Comparative Example B17: Attempt to hydrolyze sugarcane bagasse with Sulphonated Polystyrene (Negative Control 2)
[0356] Sugar cane bagasse (12.5% g H2O / g wet bagasse, with a dry matter composition: 39.0% g glucan / g dry biomass, 17.3% g xylan / g dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extracts / g of dry biomass, 24.1% of lignin g / g of dry biomass, and 3.1% of ash g / g of dry biomass) was cut, in such a way that the maximum particle size was not greater than 1 cm . To a 15 ml cylindrical glass reaction flask, 0.52 g of the sugarcane bagasse sample, 0.55 g of sulfonated polystyrene ('Amberlyst © 15, acid functionalization: 4.6 mmol / g, moisture content: 10.8% g H2O / g dispensed catalyst), and 1.8 mL deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for six hours. After the reaction, the product mixture was separated following the procedure described in Examples 42-45. The constant first order rate for converting xylan to xylose was determined to be 0.1 / h. The first order rate for the constant conversion of soluble glucan to oligo-, di-, and monosaccharides was determined to be <0.01 / hr. The average degree of polymerization of the residual cellulose was determined to be DOPN> 300 AHG units, which indicates little or no digestion of crystalline cellulose in the biomass sample. Short chain oligosaccharides were not detected. Unlike the digestion products represented in Figure (1), the residual biomass exhibited little or no structural reduction in particle size. Comparative Example B18: Attempt to hydrolysis sugarcane bagasse with cross-linked polyacrylic acid (Negative control 3)
[0357] Sugar cane bagasse (12.5% g H2O / g wet bagasse, with a dry matter composition: 39.0% g glucan / g dry biomass, 17.3% g xylan / g of dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extracts / g of dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g ash / g dry biomass) was cut, in such a way that the maximum particle size was not greater than 1 cm. To a 15 ml vial of cylindrical glass reaction was added: 0.50 g of the sugarcane bagasse sample, 0.50 g of polyacrylic acid resin beads (IRC86 Amberlite®, acid functionalization: 10, 7 mmol / g, the initial moisture content: 5.2% g H2O / g catalyst dispensed) and 1.8 mL deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for six hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The constant first order rate for converting xylan to xylose was determined to be <0.05 / hr. The first order rate for the constant conversion of soluble glucan to oligo-, di-, and monosaccharides was determined to be <0.001 / hr. The average degree of polymerization of the residual cellulose was determined to be DOPN> 300 AHG units, which indicates little or no digestion of crystalline cellulose in the biomass sample. Short chain oligosaccharides were not detected. Unlike the digestion products represented in Figure (1), the residual biomass exhibited little or no structural reduction in particle size. Comparative Example B19: Attempt to hydrolysis the sugarcane bagasse with a non-acidic ionomer as prepared in Example 2 (Negative Control 4)
[0358] Sugarcane bagasse (12.5% g H2O / g wet bagasse, with a dry matter composition: 39.0% g glucan / g dry biomass, 17.3% g xylan / g dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extracts / g of dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g gray / g dry biomass) was cut in such a way that the maximum particle size was not greater than 1 cm. To a 15 ml cylindrical reaction glass vial was added: 0.50 g of the sugarcane bagasse sample, 0.50 g of poly [styrene-co-3-methyl-l- (4-vinyl -benzyl) -3H-imidazole-1-io -co-divinylbenzene] chloride (Catalyst as described in Example 2, acid functionalization: 0.0 mmol / g, moisture content: 4.0% g of H2O / g polymer dispensed), and 1.8 mL of deionized H2O. The reagents were mixed carefully with a glass stirring rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compressed to produce a solid reagent cake. The glass reactor was sealed with a phenolic cap and incubated at 115 ° C for six hours. After the reaction, the product mixture was separated following the procedure described in Examples 42 - 45. The first order rate constant for the conversion of xylan to xylose was determined to be <0.001 / hr. No detectable amounts of soluble oligo-, di-, and monosaccharides were observed. It was determined that the average degree of polymerization of the residual cellulose was DOPN> 300 AHG units, which indicates little or no digestion of crystalline cellulose in the biomass sample. Short chain oligosaccharides were not detected. In contrast to the digestion products represented in Figure (1), the residual biomass appeared physically without changing the form of entry.

权利要求:
Claims (6)
[0001]
1. Composition characterized by the fact that it comprises: one or more saccharides; and a polymer; wherein the polymer is selected from the group consisting of: poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; 3-ethyl-1- (4-vinylbenzyl) -3H-imidazole-1-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -3H-imidazole-1-iodide-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -3H-imidazole-1-bromide-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -3H-imidazol-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-benzoimidazole-1-formate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-nitrate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-chloride-co-3-methyl-1- (4-vinylbenzyl) -3-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-bromide-co-3-methyl-l- (4-vinylbenzyl) -3-phenimidazole-bisulfate-co- divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-iodide-co-3-methyl-l- (4-vinylbenzyl) -3-phenimidazole-bisulfate-co- divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-bisulfate-co-3-methyl-1- (4-vinylbenzyl) -3i-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1- (4-vinylbenzyl) -pyridine-acetate-co-3-methyl-1- (4-vinylbenzyl) -3-imidazole-bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-4-methyl-4- (4-vinylbenzyl) -morpholine-4-formate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triphenyl- (4-vinylbenzyl) -phosphono chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triphenyl- (4-vinylbenzyl) -phosphono bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic -co-triphenyl- (4-vinylbenzyl) -phosphono acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1-methyl-1- (4-vinylbenzyl) -pipererdin-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1-methyl-1- (4-vinylbenzyl) -pipererdin-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 1-methyl-1- (4-vinylbenzyl) -pipererdin-1-acetate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co- 4- (4-vinylbenzyl) -morpholinee-4-oxide-co-divinyl benzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium chloride-co-divinylbenzene]; triethyl- (4-vinylbenzyl) -ammonium bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-triethyl- (4-vinylbenzyl) -ammonium acetate-co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-4-boronyl-1- (4-vinylbenzyl) -pyridine chloride-co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-1- (4-vinylphenyl) methylphosphonic acid -co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazol-1- bisulfate-co-1- (4-vinylphenyl) methylphosphonic acid -co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-1- (4-vinylphenyl) methylphosphonic acid -co-divinylbenzene]; poly [styrene-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-nitrate-co-1- (4-vinylphenyl) methylphosphonic acid -co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine chloride-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylchloride-co-1-methyl-2-vinyl-pyridine acetate-co-divinylbenzene]; 4- (4-vinylbenzyl) -morpholinae-4-oxide-co-divinyl benzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-4-vinylphenylphosphonic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-3-carboxymethyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) -isophthalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) - isofithalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co-5- (4-vinylbenzylamino) - isofithalic acid -co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid-co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-chloride-co-divinylbenzene]; co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-bisulfate-co-divinylbenzene]; poly [styrene-co- (4-vinylbenzylamino) -acetic acid- co-3-methyl-1- (4-vinylbenzyl) -3H-imidazole-1-acetate-co-divinylbenzene]; poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole chloride-co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenyl phosphone chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole chloride-co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenyl phosphone chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole bisulfate-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole bisulfate-co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenyl phosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole acetate-co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenyl phosphone acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole acetate-co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenyl phosphone acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine chloride-co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine bisulfate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylmorpholine acetate-co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene) poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole chloride-co-divinyl); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylmethylimidazole nitrate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole chloride-co-divinylbenzene); vinylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzylmethylimidazole acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenesulfonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzene); poly (styrene-co-4-vinylbenzenophosphonic acid -co-vinylbenzyltriphenylphosphono acetate-co-divinylbenzene); poly (butyl-vinylimidazole chloride-co-butylimidazole bisulfate-co-4-vinylbenzenesulfonic acid); poly (butyl vinylimidazole bisulfate-co-butylimidazole bisulfate-co-4-vinylbenzenesulfonic acid); poly (benzyl acid alcohol-co-4-vinylbenzyl alcohol sulfonic -co-vinylbenzyltriphenylphosphono chloride-co-divinylbenzyl alcohol); and poly (benzyl acid alcohol-co-4-vinylbenzyl alcohol sulfonic -co-vinylbenzyltriphenylphosphono bisulfate-co-divinylbenzyl alcohol).
[0002]
2. Composition according to claim 1, characterized by the fact that the composition further comprises a solvent.
[0003]
3. Composition according to claim 2, characterized by the fact that the solvent comprises water.
[0004]
Composition according to any one of claims 1 to 3, characterized in that the one or more saccharides are one or more monosaccharides, or one or more oligosaccharides, or a mixture thereof.
[0005]
Composition according to any one of claims 1 to 4, characterized by the fact that the one or more saccharides are two or more saccharides, wherein at least one of the two or more saccharides is a C4-C5 monosaccharide, and at least one of the two or more saccharides is an oligosaccharide.
[0006]
Composition according to any one of claims 1 to 4, characterized by the fact that the one or more saccharides are selected from the group consisting of glucose, galactose, fructose, xylose, mannose and arabinose.

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法律状态:
2016-12-06| B15I| Others concerning applications: loss of priority|Free format text: PERDA DAS PRIORIDADES US 61/522,351 E US 61/447,311, DE 11/08/2011 E 28/02/2011 RESPECTIVAMENTE, REIVINDICADAS NO PCT/US2012/026820, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 167O, ITEM 28 DO ATO NORMATIVO 128/97 E NO ART. 29 DA RESOLUCAO INPI-PR 77/2013. ESTAS PERDAS SE DERAM PELO FATO DE O DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DE ENTRADA NA FASE NACIONAL SER DISTINTO DAQUELES QUE DEPOSITARAM OS PEDIDOS ANTERIORES CUJA PRIORIDADE E REIVINDICADA E NAO FORAM APRESENTADOS DOCUMENTOS DE CESSAO NO PRAZO LEGAL (60 DIAS APOS A ENTRADA DA FASE NACIONAL DO BRASIL), CONFORME AS DISPOSICOES PREVISTAS NA LEI 9.279 DE 14/05/1996 (LPI) ART. 166O, ITEM 27 DO |

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2017-02-07| B12F| Other appeals [chapter 12.6 patent gazette]|

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2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-04-16| B25D| Requested change of name of applicant approved|Owner name: MIDORI USA, INC. (US) |

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2019-04-30| B25A| Requested transfer of rights approved|Owner name: CADENA BIO, INC. (US) |

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2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-27| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-07-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161447311P| true| 2011-02-28|2011-02-28|

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US61/447,311|2011-02-28|

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US201161522351P| true| 2011-08-11|2011-08-11|

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US61/522,351|2011-08-11|

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PCT/US2012/026820|WO2012118767A1|2011-02-28|2012-02-27|Polymeric acid catalysts and uses thereof|

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