process for the preparation of a polysaccharide derivative, and, polysaccharide derivative

专利摘要:
PROCESS FOR THE PREPARATION OF A POLYESACARIDE DERIVATIVE, AND, POLYSACARIDE DERIVATIVE. The invention relates to a process for the preparation of a polysaccharide derivative, which comprises the stages of: (a) contacting at least one polysaccharide with at least one polysaccharide swelling agent, at a temperature of a maximum of 70 ° C; and (b) subsequently contacting the product from stage (a) with at least one aromatic isocyanate; thereby preparing a polysaccharide derivative.
公开号:BR112014032147B1
申请号:R112014032147-7
申请日:2013-06-05
公开日:2020-12-22
发明作者:Christopher Phanopoulos；Servaas Holvoet；Tugba Vardareli；Steve Diamanti
申请人:Huntsman International, Llc；
IPC主号:

专利说明:

[001] The present invention relates to processes for the preparation of polysaccharide derivatives and the polysaccharide derivatives thus obtained.
[002] Cellulose is a hard, fibrous, water-insoluble substance that can be found in the protective (cellular) wall of plants. It is a polysaccharide, which is mainly composed of [beta] -D-glucopyranose units linked by 1-4 glycosidic bonds. From a structural perspective, cellulosic chains are arranged in microfibrils during crystallization, with the formation of intermolecular hydrogen bonds of chain hardening. Different crystalline cellulose allomorphs are known.
[003] The hydroxyl groups on cellulosic substrates are involved in a number of intra- and intermolecular hydrogen bonds and, in general, have limited reactivity as nucleophilic moieties. As a consequence, the chemical derivation of these hydroxyl groups is extremely difficult. Even in relation to highly reactive molecules (such as, for example, isocyanates), these hydroxyl groups do not show or show very little reactivity. Another disadvantage of these cellulosic materials is their high melting point, usually higher than the thermal decomposition temperature, which limits their potential for derivation in the liquid phase.
[004] Traditional approaches in chemical cellulose derivation use chemically and / or physically severe conditions (chemicals, temperature, pressure, pH, ...) in a way to dissolve or to derive cellulose. This impacts the mass structure and related properties (such as crystallinity) of the substrates. These current solutions were mainly focused on decreasing or eliminating the hydrogen bonding pattern on the cellulosic substrate, as discussed below.
[005] Sometimes, the problem is merely ignored. In these ecuqu. c egnwnqug rqfg cVwct eqoq woc “non-reactive load”.
[006] One option is to alkoxylate the cellulosic substrate, so that its solubility and compatibility are increased with the derivative agent. Alkoxylation impacts crystallinity, increases capital costs and, in addition, is associated with EHS risks.
[007] Another possibility is the use of mono-, di- and / or oligosaccharides, which have different solubility characteristics. However, such use is limited, in some applications, when the mass properties of cellulosic substrates are required (for example, composites).
[008] Another option is to break the hydrogen bonding network.
[009] The frequently applied methods chemically digest cellulosic substrates through sulfite or alkaline processes (caustic soda, diluted NaOH), at high temperatures, in pressure vessels (degradation, lower molecular weight, decreased crystallinity). However, the aqueous medium or residual moisture, which is often linked to the hydrogen network, is incompatible with isocyanate chemistry and causes side reactions. In addition, residues from the digestion medium (for example, Na and / or K cations) can be released and can cause side reactions with isocyanates (for example, isocyanurates). In addition, the degradation of the structure leads to a deterioration of cellulosic properties.
[0010] The hydrogen bonding network can also be partially or completely destroyed through the use of mechanical treatments (for example: crushing, grinding, etc.), in which the mechanical energy can disrupt the microfibrils, so that the cellulosic substrate is then degraded. This then leads to reduced molecular weight and higher amorphous content. However, mechanical treatments damage the structure of the cellulosic mass, which, in turn, can negatively affect molecular weight, fiber strength and hardness, etc.
[0011] Alternatively, the steam explosion can also be applied to break up the cellulosic substrate under severe pressure and temperature conditions. This procedure also requires an extra drying stage and, in addition, it is known to reduce the crystalline content of the substrates.
[0012] Thus, there remains a need for processes for the preparation of functionalized polysaccharides, which overcome one or more of the issues mentioned above. It is an object of the present invention to provide a process for the preparation of a functionalized polysaccharide. It is also an object of the invention that a functionalized polysaccharide is provided, while maintaining, or only minimally reduced, the mass properties of the polysaccharide, such as crystallinity.
[0013] The present inventors have now found, surprisingly, that one or more of these objects can still be obtained through a process for the preparation of a polysaccharide derivative according to the invention. The polysaccharide derivative is obtained by pre-contacting the polysaccharide with a compound, before adding an aromatic isocyanate for functionalization, said pre-contacting stage being carried out at a temperature of, at most, 70 ° C. The polysaccharide derivative may comprise pendant free isocyanate groups, which allow the polysaccharide to be further derived, and / or improve the compatibility of the polysaccharide particles with isocyanate-based liquids. Polysaccharide derivatives can subsequently be used in different applications, through additional reaction / derivation with other isocyanate reactive functionalities, such as substrates, special chemicals, and polyurethane components.
[0014] The present invention comprises a process for the preparation of a polysaccharide derivative, the process comprising the stages of: (a) contacting at least one polysaccharide with at least one polysaccharide swelling agent, preferably selected from of the group, which comprises sulfoxides, formamides, acetamides, pyrrolidones, pyridines, imidazoles and mixtures thereof, at a maximum temperature of 70 ° C: and (b) subsequently, contact the product from stage (a) with at least an aromatic isocyanate; thereby preparing a polysaccharide derivative.
[0015] Preferably, the polysaccharide derivative, prepared in accordance with the present invention, comprises the reaction product of: (a) at least one polysaccharide with a degree of polymerization of at least 5; and (b) at least one aromatic isocyanate; and the CI crystallinity index of the polysaccharide derivative, as measured by XRD, is at least 5%.
[0016] The dependent and independent claims expose the particular and preferred features of the invention. The characteristics of the dependent claims may be combined with characteristics of the independent claims or other dependent claims, as appropriate.
[0017] The above features and other features and advantages of the present invention will become apparent from the following detailed description, which illustrates, by way of example, the principles of the invention.
[0018] Figure 1 represents a cellulose X-ray diffraction spectrum (Avicel PH-101).
[0019] Figure 2 represents an X-ray diffraction spectrum of corn starch.
[0020] It should also be understood that this invention is not limited to the particular modalities described, as such modalities can, of course, vary. It should also be understood that the terminology used here is not intended to be limiting, as the scope of the present invention will be limited only by the appended claims.
[0021] Vcl eqoq cswk wucfq. cu forocu ukpiwnctgu “wo”, “woc”. g "o" includes both singular and plural referents, unless the context clearly dictates otherwise. C ViVwno fg gxgmplo. “Wo kuoekcpcvo group” ukipkhkea an isocyanate group or more than an isocyanate group.
[0022] Qu rgroou “eoorrggpfgpfo”. "Eoorrggpfg". g "eoorrggpfkfo de", as used herein, u «ukp» pkoou fg "kpelwkpfo". “Kpelwk” ow “eopvgpfo”. "Eopvfio". g also include open ended members, and do not exclude additional members, elements or stage of the method, not mentioned. It should also be appreciated that the terms “eoorrggpfgpfo”. "Eoorrggpfg". and “eoorrggpfkfou fg”. vcku eooo cswk wucfou. comprise the terms "eopukuvkpfo fg". "Eopukuvg". g “eopukute fg” 0
[0023] Throughout this rgfkfo. the “egrec fg” vgroo. fi used to indicate that a value includes the standard deviation or error for the device or method being employed to determine the value.
[0024] Vcku eooo cswk wucfou. or called “'go rguo”. “'Go rguo” “rgrcentual em rguo”. ow “rgregpvwcl go rguo”. u «wucfou interchangeably.
[0025] The citation of numerical ranges by the end points includes all the whole numbers and, when appropriate, the fractions within that range (for example, from 1 to 5 includes 1, 2, 3, 4 when referring to, for example , a number of elements, and can also include 1.5, 2, 2, 75 and 3.80, when referring to, for example, measurements). The endpoint quote also includes the endpoint values themselves (for example, from 1.0 to 5.0 includes both 1.0 and 5.0). Any numeric range mentioned in this is intended to include all the sub-ranges included herein.
[0026] All references cited in this application are incorporated into it, by reference, in their entirety. In particular, the teachings of all the references specifically mentioned here must be incorporated, by way of reference.
[0027] Unless otherwise defined, all terms used in the description of the invention, including technical and scientific terms, have the meaning, as commonly understood by one of ordinary skill in the technique, to which this invention belongs . By way of additional guidance, the term definitions are included herein, so that the teachings of the present invention can be better appreciated.
[0028] The Vgtoq “cnswüc” eqoq wo itwrq. qw rcrtg fg wo itwrq, Vcn as used herein, refers to a straight or branched (straight) or cyclic hydrocarbon, without unsaturation site, preferably having at least 4 carbon atoms in the chain. When a subscript is used here following a carbon atom, the subscript refers to the number of carbon atoms that the named group can contain. Thus, for example, C1-20 alkyl comprises alkyl of 1 to 20 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and their chain isomers, hexyl and their chain isomers, heptyl and their chain isomers, octyl and their isomers chain, nonyl and its chain isomers, decila and its chain isomers, undecyl and its chain isomers, dodecyl and its chain isomers.
[0029] Q Vgtoq “cnswgpüc”, eqoq wo itwrq qw rcrtg fg wo itwrq, Vcn as used herein, refers to a straight or branched or cyclic hydrocarbon, with at least one site (in the usual way from 1 to 3, preferably 1) unsaturation, i.e. carbon-carbon, sp2 double bond, preferably having at least 4 carbon atoms in the chain. The double bond can be in a cis or trans configuration. C1-20 alkenyl means an alkenyl of 1 to 20 carbon atoms.
[0030] As used herein, q Vgtoq "ekelqclswilc C3-6", go uk oguoq or as part of another substituent, refers to a saturated or partially unsaturated cyclic alkyl radical, containing from about 3 to about 6 carbon atoms. Examples of C3-6 cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
[0031] Vcl eqoq cswk wucfq. q Vgtoq “ctklc CÔ-IO” .go itself or as part of another substituent, refers to an aromatic, polyunsaturated hydrocarbyl group, having a single ring (ie, phenyl) or multiple aromatic rings fused from one combined (eg naphthyl) or covalently bonded, typically containing 6 to 10 carbon atoms, where at least one ring is aromatic. Arila C6-10 is also intended to include the partially halogenated derivatives of the carboxylic systems, listed here. Non-limiting examples of aryl include phenyl, naphthyl, indanyl, or 1,2,3,4-tetrahydro-naphthyl.
[0032] As used herein, the term "ctklc CÔ-IO - CI-Ô alkyl" .go uk same or as part of another substituent, refers to a C1-ô alkyl group as defined herein, where a hydrogen atom is replaced by C10-aryl, as defined herein. Examples of the C1-ô alkyl aryl radicals include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3- (2-naphthyl) -butyl, and the like.
[0033] In the passages that follow, different aspects of the invention are defined in greater detail. Each aspect thus defined can be combined with any other aspect or aspects, unless clearly indicated otherwise. In particular, any characteristic indicated as being preferred or advantageous, can be combined with any other characteristic or characteristics, indicated as being preferred or advantageous.
[0034] The reference, throughout this report, to “woc oqfcnkfcfg” qw “woc oqfcnkfcfg” uignil'iec swe a particular feature, structure or feature described in connection with the modality is included in at least one modality of the present invention . Thus, the appearances of the ltcugu "" go "woc" oqfcnifcfg "" qw "go" woc oqfcnifcfg "." Go various locations throughout this report, do not necessarily all refer to the same modality, but they can. Furthermore, the particular characteristics, structures or characteristics can be combined in any suitable way, as would be evident to a person skilled in the art, from this description, in one or more modalities. Furthermore, although some modalities described herein include some, but not other characteristics included in other modalities, combinations of characteristics of different modalities are considered to be within the scope of the invention, and constitute different modalities, as would be understood by those skilled in the art. technical. For example, in the appended claims, any of the claimed modalities can be used, in any combination.
[0035] The present invention comprises a process for the preparation of a polysaccharide derivative, the process comprising the stages of: (a) contacting at least one polysaccharide with at least one compound, at a temperature of at most 70 ° C, preferably at room temperature; and (b) subsequently, contacting the product from stage (a) with at least one aromatic isocyanate; thereby preparing a polysaccharide derivative.
[0036] The at least one compound can be any polysaccharide swelling agent, essentially in the absence of water. The at least one compound can be any polysaccharide swelling agent, which is not reactive to isocyanate. Preferably, the at least one compound is selected from the group, which comprises sulfoxides, formamides, acetamides, pyrrolidones, pyridines, imidazoles and mixtures thereof.
[0037] In yet another embodiment, the present invention comprises a process for the preparation of a polysaccharide derivative, the process comprising the stages of: (a) contacting at least one polysaccharide with at least one compound, selected from the group , which comprises sulfoxides, formamides, acetamides, pyrrolidones, pyridines, imidazoles and mixtures thereof, at a temperature of a maximum of 70 ° C, and preferably at room temperature, and (b) subsequently, the reaction of the product from stage (a) with at least one aromatic isocyanate, thereby preparing a polysaccharide derivative.
[0038] Preferably, the at least one compound is present in an amount of at least 25% by weight, preferably at least 50%, and preferably at least 75%, for example at least 90%, for example at least 95%, based on the total weight of the combined polysaccharide and compound.
[0039] In still a preferred embodiment, the at least one polysaccharide in stage (a) is present in an amount in the range of from 0.5 to 99.0% by weight, based on the total weight of at least least one polysaccharide and at least one compound combined. Preferably, the at least one polysaccharide in stage (a) is present in an amount in the range of from 2.0 to 70.0 by weight, and even more preferably, in a range of from 5.0 to 50.0% by weight, based on the total weight of the at least one polysaccharide and at least one compound combined.
[0040] Stage (a) of the process according to the invention comprises contacting at least one polysaccharide with at least one compound, which causes swelling, but which does not react with isocyanates, preferably said compound being selected from of the group, which comprises sulfoxides, formamides, acetamides, pyrrolidones, pyridines, imidazoles, and mixtures thereof. Said stage is performed at a temperature below 70 ° C, and preferably at a temperature below 60 ° C, and even more preferably at a temperature below 50 ° C, and preferably at a temperature below 40 ° C, and preferably at room temperature. As used herein, the term "VgorgtcVwtc codkgpVg" is used at a temperature of from 15 to 35 ° C.
[0041] Stage (a) can cause swelling of at least one polysaccharide. Without being limited by theory, intumescence can make surface hydroxyl moieties more accessible for reaction with derivative agents. Preferably, such a swelling procedure is a reversible stage and allows for complete regeneration of the crystalline structure.
[0042] As used herein, q Vetoq "uwnfózkfq" refers to compounds, which comprise a sulfur atom covalently linked to three atoms, at least one of which is an oxygen atom; the formal oxidation state of said sulfur atoms is (IV). The preferred sulfoxides have the general structure of formula (1): S (O) R1R2 (1) (c) that R1 and R2 are independently selected from the group, which comprises hydrogen, C1-20 alkyl, C1-20 alkenyl, C6-10 aryl, C3-6 cycloalkyl, and C6-10 aryl - C1-6 alkyl, optionally substituted by heteroatoms. Examples of preferred R1 and R2 include C1-20 alkyl, phenyl and benzyl. Preferably, the at least one compound is dimethyl sulfoxide (DMSO).
[0043] As used herein, the term "formamide" refers to compounds, which comprise the formamide group -NC (O) H. Preferred formamides have the general formula of formula (2): HC (O) NR21R22 (2) where R21 and R22 are independently selected from the group, which comprises hydrogen or C1-20 alkyl. In still one embodiment, the at least one compound is N, N-dimethyl formamide (DMF).
[0044] As used herein, the term "acetamide" refers to compounds, which comprise the functional group -NC (O) CH3. Preferred acetamides have the general structure of formula (3): HC (O) NR31R32 (3) in which R31 and R32 are independently selected from the group, which comprises hydrogen or C1-20 alkyl. In still one embodiment, the at least one compound is N, N-dimethyl acetamide (DMAc).
[0045] As used herein, the term "pyrrolidones" refers to the compound with the chemical formula C4H7NO, optionally substituted by C1-20 alkyl and / or halogens.
[0046] As used herein, the term "pyridines" refers to the compound with the chemical formula C5H5N, optionally substituted by C1-20 alkyl and / or halogens.
[0047] As used herein, the term "imidazole" refers to the compound with the chemical formula C3H4N2, optionally substituted by C1-20 alkyl and / or halogens.
[0048] In still a preferred embodiment, the at least one compound is selected from the group, which comprises: dimethyl sulfoxide, diethyl sulfoxide, ethyl methyl sulfoxide, N, N-dimethyl formamide, N, N-diethyl formamide , N, N-ethyl methyl formamide, N-methyl-pyrrolidone, pyridine, bromo-pyridine, chloro-pyridine, N, N-dimethyl acetamide, N, N-diethyl acetamide, N, N-ethyl methyl acetamide, 1.3 -dimethyl-2-imidazolidinone, imidazolidinone, 1-methyl-2-imidazolidinone, 1-ethyl-2-imidazolidinone, 1-allyl-3-methylimidazole chloride, 1-butyl-3-methyl imidazole chloride, 1- ethyl-3-methyl imidazolium, and mixtures thereof. In still a preferred embodiment, the compound is dimethyl sulfoxide (DMSO).
[0049] In yet an alternative embodiment, the at least one compound can be any compound, which is not reactive to isocyanate. Preferably, the at least one compound is any compound, which does not break strong hydrogen bonds. For example, the at least one compound can be an ionic liquid. Preferably, the at least one compound is essentially free of any compounds, which are reactive to isocyanate. Preferably, the at least one compound is essentially free of any compounds, which break strong hydrogen bonds. For example, the at least one compound can be essentially free of LiCl.
[0050] In still a preferred embodiment, the at least one compound is anhydrous. Preferably, the at least one compound is anhydrous DMSO. In still a preferred embodiment, the water content in at least one polysaccharide, at least one isocyanate and at least one compound is at most 0.5% by weight, preferably at most 0, 4% by weight, and even more preferably, at most, 0.2% by weight.
[0051] In still a preferred embodiment, stage (a) is preceded by the drying stage of the polysaccharide, preferably under vacuum.
[0052] In still some embodiments, this drying stage is carried out for at least 0.5 hours, and preferably at least 1 hour, more preferably at least 2 hours, still more preferably at least 6 hours, and at least one hour. preferably about 12 hours.
[0053] In still a preferred embodiment, stage (a) is performed for a period of time of at least 30 minutes, before stage (b). Preferably, stage (a) comprises contacting at least one polysaccharide with at least one compound for at least 3 hours, and more preferably for at least 2 hours, and even more preferably for at least 1 hour . In still some embodiments, stage (a) comprises contacting at least one polysaccharide with at least one compound, over a period of time in the range of from 0.5 to 24 hours, more preferably from 0.5 to 24 hours. 12 hours, and more preferably 0.5 to 3 hours. The aforementioned time periods are the preferred time periods for temperatures of a maximum of 50 ° C. For higher temperatures, stage (a) may be shorter. It is further preferred that the time period and temperature in stage (a) do not result in a complete dissolution of the polysaccharide. For example, at a temperature from 50 ° C to 60 ° C, stage (a) is carried out for a period of time of a maximum of 2 hours, for example, 0.5 to 2 hours. Preferably, at a temperature of from 60 ° C to 70 ° C, stage (a) is carried out for a period of time of a maximum of 1 hour, for example from 0.5 to 1 hour.
[0054] Stage (b) of the process according to the invention comprises the reaction of the product of stage (a) with at least one aromatic isocyanate. For example, stage (b) of the process according to the invention comprises contacting or mixing the product of stage (a) with at least one aromatic isocyanate.
[0055] Preferably, stage (b) is carried out in contact with at least one compound as stage (a).
[0056] In still some embodiments, stage (B) comprises contacting, mixing and / or reacting the product of stage (a) with at least one aromatic isocyanate for at least 15 minutes, and preferably for at least minus 30 minutes, and even more preferably for at least 1 hour, and even more preferably for at least 4 hours.
[0057] In still some modalities, stage (b) comprises contacting, mixing and / or reacting the product of stage (a) with at least one aromatic isocyanate, over a period of time in a range from 15 minutes to 24 hours, and preferably from 30 minutes to 12 hours, and even more preferably from 1 to 12 hours.
[0058] In still some embodiments, the temperature in stage (b) is between 25 and 125 ° C, and even more preferably from 25 to 80 ° C, and even more preferably from from 25 to 50 ° C.
[0059] In still some preferred embodiments, the mixture in stage (b) is stirred, for example, stirred or shaken.
[0060] In still some modalities, stage (b) comprises mixing the product of stage (a) with at least one catalyst. Preferably, the catalyst is an organometallic catalyst. Any other stage can be performed in the presence of a catalyst.
[0061] In still some modalities, the catalyst is an organometallic catalyst. In these modalities, the catalyst comprises an element selected from the group, which comprises tin, iron, lead, bismuth, mercury, titanium, hafnium, zirconium, and combinations thereof. In still certain embodiments, the catalyst comprises a tin catalyst. Suitable tin catalysts, for the purposes of the present invention, can further be selected from tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin tin hexanoate (II) and tin laurate (II). In yet another embodiment, the organometallic catalyst comprises dibutyl tin dilaurate, which is a dialkyl tin (IV) salt of an organic carboxylic acid. The organometallic catalyst can also comprise other dialkyl tin (IV) salts of organic carboxylic acids, such as dibutyl tin diacetate, dibutyl tin maleate and dioctylt tin diacetate. Specific examples of suitable organometallic catalyst, for example dibutyl tin dilaurates, for the purposes of the present invention, are commercially available from Air Products and Chemicals Inc., under the trademark DABCO®. Preferred catalysts according to the invention are dibutyl tin dilaurate, dibutyl tin diacetate, tin dioctyl diacetate, and tin octoate.
[0062] Non-limiting examples of other suitable catalysts can be selected from the group, which comprises iron (II) chloride; zinc chloride; tin octoate; tris (dialkylaminoalkyl) -s-hexahydroxyriazines, which include tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine; tetraalkyl ammonium hydroxides, which include tetramethyl ammonium hydroxide; alkali metal hydroxides, which include sodium hydroxide and potassium hydroxide; alkali metal alkoxides, which include sodium methoxide and potassium isopropoxide; and the alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and / or side OH groups; triethyl amine, N, N, N ', N'-tetramethylethylene diamine, N, N-fkogVücokpqrtqrücokpc. P.P. P P P ”-pentamethyldipropylenetriamine. tris (dimethylaminopropyl) amine, N, N-dimethyl piperazine, tetramethylimino-bis (propylamine). dimethylbenzylamine. trimethyl amine. triethanolamine. N.N-diethyl ethanolamine. N-methyl pyrrolidone. N-methyl morpholine. N-ethyl morpholine. bis (2-dimethylamino-ethyl) ether. N.N-dimethylcyclohexylamine (DMCHA). N. N. N '. N '. P ”-pentamethyldiethylene triamine, 1,2-dimethylimidazole, 3- (dimethylamino) propylimidazole; N.N. N-dimethylaminopropyl hexahydrotriazine. potassium acetate, N, N, N-trimethyl isopropyl amine / formate, and combinations thereof. It should also be appreciated that the catalyst component can further include any combination of two or more of the aforementioned catalysts.
[0063] Preferably, the catalyst is present in an amount of at least 10 ppm, for example at least 0.01% by weight, for example at least 0.20% by weight, the% in weight being based on the total weight of the isocyanate.
[0064] In still some modalities, the catalyst is present in a maximum of 5% by weight, based on the weight of the isocyanate.
[0065] In still some embodiments of the invention, the process according to the invention comprises one or more additional stages, such as the washing stages, drying stages, or discharge stages.
[0066] The process of the present invention further provides a polysaccharide derivative, which comprises the product of the reaction of at least one polysaccharide with at least one aromatic isocyanate, wherein the at least one polysaccharide preferably has a degree of polymerization of at least 5, and the polysaccharide derivative has a crystallinity index (CI), as measured by XRD, of at least 5%.
[0067] As used here, the term “fgtkxcfq fg rqnkuucecrífgq” ended. “Rqnkuucecrífgq oqfkfiecfq” g “rqnkuucecrífgq hwpekqpcnkzcfq” u «q ukp» pkoqu g are used interchangeably and refer to an isocyanate-functionalized polysaccharide. The reaction product can then be obtained by adding, reacting, contacting or mixing the different components.
[0068] According to one embodiment, the polysaccharide derivative, obtained through the process of the present invention, comprises a polysaccharide backbone and one or more pendant groups, connected to the polysaccharide backbone through a carbamate -OC link (= O) -NH-. Such a carbamate bond can be further formed by reacting a free isocyanate group -N = C = O with a hydroxyl group on a polysaccharide backbone.
[0069] According to yet another embodiment, the polysaccharide derivative, obtained through the process of the present invention, comprises a polysaccharide backbone and one or more pendant groups, connected to the polysaccharide backbone through an allophanate bond - NH- C (= O) -NH-. Such a urea bond can be formed by reacting a free isocyanate group -N = C = O with an amine group on a polysaccharide backbone.
[0070] According to yet another embodiment, the polysaccharide derivative, obtained through the process of the present invention, comprises a polysaccharide backbone and one or more pendant groups, linked to the polysaccharide backbone through an -NH- allophanate C (= O) -N (- C (= O) -O -) -. Such an allophanate bond can be formed by reacting a free isocyanate group -N = C = O, with a urethane group on a polysaccharide backbone.
[0071] According to yet another embodiment, the polysaccharide derivative, obtained through the process of the present invention, comprises a polysaccharide backbone and one or more pendant groups, linked to the polysaccharide backbone through a biuret -NH link - C (= O) -N (-C (= O) -NH -) -. Such a biuret bond can be formed by reacting a free isocyanate group N = C = O with a urea group on a polysaccharide backbone.
[0072] Preferably, the one or more pendant groups comprise at least one free isocyanate group -N = C = O, which can be further used for further functionalization. Preferably, the degree of polymerization of the polysaccharide backbone is at least 5. Preferably, the CI crystallinity index of the polysaccharide derivative, as measured by XRD, is at least 5%.
[0073] NCO content of the polysaccharide derivative can be in a range of from 0% to 10%, as measured according to DIN 53185. In still some embodiments, the NCO content of the polysaccharide derivative is at least 0.2%. For example, the NCO content can be in a range from 0.2% to 5.0%, for example from 0.2% to 3.0%.
[0074] Go eqoq cswk wucfq. q Vgtoq “rqnkuucecrífgq” refers to compounds, which comprise at least 5 subunits of saccharide monomer, joined together by means of glycosidic bonds.
[0075] Preferably, the at least one polysaccharide has a degree of polymerization of at least 10, more preferably at least 20, even more preferably at least 50, for example at least 100, for example at least 150, for example at least 200, for example at least 500.
[0076] At least one polysaccharide can be natural or synthetic. The at least one polysaccharide can be crude or purified. The at least one polysaccharide can be original or (partially) pre-derived or modified. The at least one polysaccharide can be linear, branched or cyclic. The at least one polysaccharide can be a homopolysaccharide (also called a homoglycan) or a heteropolysaccharide (also called a heteroglycan).
[0077] Preferably, the at least one polysaccharide is based on hexose, that is, the at least one polysaccharide comprises at least one hexose subunit. Even more preferably, the at least one polysaccharide comprises at least 50% by weight of hexose subunits, based on the total weight of the polysaccharide, and even more preferably at least 75% by weight, even more preferably at least 90% by weight. Preferably, the at least one polysaccharide is based on cyclic hexose.
[0078] In still a preferred embodiment, the at least one polysaccharide comprises at least one glucose subunit. Preferably, the at least one polysaccharide comprises at least 50% by weight of glucose subunits, based on the total weight of the polysaccharide, and even more preferably at least 75% by weight, and even more so. at least 90% by weight is preferred. The glucose subunits can be modified glucose subunits, for example amino-glucose subunits, with a substituent at the C2 or C3 position.
[0079] In still some modalities, the at least one polysaccharide is selected from the group, which comprises: cellulosic compounds; starches (such as amylose or amylopectin or mixtures thereof); agarose, alginic acid; alguronic acid; alpha glucan; amylopectin; amylose; arabinoxylan; beta-glucan; callose; capsulane; carrageenan; cellodextrin; cellulin; chitin; chitosan; chrysolaminarine; curdlan; cyclodextrin; DEAE-sepharose; dextran; dextrin; alpha-cyclodextrin; ficol; fructan; fucoidan; galactoglucomannan; galactomannan; gellan gum; glucan; glucomannan; glycocalix; glycogen; hemicellulose; hypromellosis; icodextrin; quefirano; laminarin; lentinan; levano; lichenin; maltodextrin; mixed-bonded glucan; mucilage; natural gum; oxidized cellulose; pramilon; pectic acid; pectin; pentaamido; peluran; polydextrrose; polysaccharide peptide; porphyran; pullulan; schizophilan; sepharose; sinistrin; sizofiran; sugammadex; welano gum; xanthan gum; xylan; xyloglucan; zymosan; glycosaminoglycans, such as glycosaminoglycan, chondroitin, chondroitin sulfate, dermatan sulfate, heparan sulfate, heparin, heprinoid, hyaluronan, keratan sulfate, restilane, sodium hyaluronate, and sulodexide; and their mixtures. In still some preferred embodiments, the at least one polysaccharide is selected from the group, which comprises cellulosic compounds and starches.
[0080] In still one embodiment, the at least one polysaccharide is a starch, selected from the group, comprising: corn starch, amylose, acetylated diamido adipate, starch, amylopectilna, cyclodextrin, dextrin, dialdehyde starch, erythronium japonicum, high fructose corn syrup, hydrogenated starch hydrosylate, hydroxyethyl starch, hydroxypropyl diamide phosphate, maltitol, maltodextrin, maltose, pentaamido, phosphate diamide phosphate, potato starch, starch, waxy maize, starch waxy potato, and mixtures thereof.
[0081] In still one modality, at least one polysaccharide is a cellulosic compound, selected from the group, comprising: cellulose, nanocellulose, silk varieties, bacterial cellulose, bamboo fiber, carboxymethyl cellulose, cellodextrin, cellophane, celluloid , cellulose acetate, cellulose acetate phthalate, cellulose triacetate, cellulosome, cotton, croscarmellose sodium, crystallate, ciethylaminoethyl cellulose, dissolved pulp, etulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl cellulose, hydroxypropylene , mercerized pulp, methyl cellulose, microbial cellulose, microcrystalline cellulose, modal (textile) nitrocellulose, parksin, peroloid, pulp, paper, rayon, sodium cellulose phosphate, supima, viscose, vulcanized fiber, wood fiber, and mixtures thereof .
[0082] In still a preferred embodiment, the polysaccharide is cellulose or starch. As used herein, q Vgtoq "eenwnque" refers to a polysaccharide, which comprises a linear chain of several hundred to over ten thousand units of D-glucose β * 3s6 + nkicfcUo
[0083] Polysaccharide derivative, obtained through the process of the present invention, comprises the product of the reaction of at least one polysaccharide with at least one aromatic isocyanate.
[0084] As used herein, the term isocyanate comprises any compound, which comprises at least one isocyanate group -N = C = O, wherein the isocyanate group can be a terminating group. Preferably, the isocyanate group is a terminating group. The isocyanate compounds are preferably polyisocyanate compounds. Suitable polyisocyanates used can be araliphatic and / or aromatic polyisocyanates, typically of the R- (NCO) type x, with x being at least 1, preferably being at least 2, and R being one aromatic group or a combined aromatic / aliphatic group. Examples of R are diphenyl methane, toluene, or groups that provide a similar polyisocyanate.
[0085] In yet another preferred embodiment, the isocyanate is a polyisocyanate. Due to the partial superficial cross-linking (intra-cross-linking and inter-interleaving between the cellulosic chains) by the polyisocyanate, the mass of the cellulosic substrate can be protected against derivation. In this way, the crystalline, rigid nature of the cellulosic backbone can be further preserved for additional applications, in which the mass properties of the cellulosic material are required (for example, for composites). Free isocyanate groups can also be used for additional functionalization or derivation. The free isocyanate groups of the polyisocyanates can also be trimerized, so that isocyanurate groups are formed.
[0086] In still a preferred embodiment, the at least one isocyanate is a polyisocyanate, selected from the group, which comprises: diphenyl methylene diisocyanate in the form of its 2,4'-, 2,2 ' - and 4,4'-isomers and mixtures thereof, mixtures of diphenyl methylene diisocyanates and oligomers thereof, or their derivatives having urethane, isocyanurate, allophanate, biuret, uretonin, uretdione and / or iminooxadiazinadione groups and mixtures thereof; toluene diisocyanates and isomer mixtures thereof; tetramethylxylene diisocyanate; 1,5-naphthalene diisocyanate; p-phenylene diisocyanate; tolidine diisocyanate; or mixtures of these organic polyisocyanates, and mixtures of one or more of these organic polyisocyanates with diphenyl methylene diisocyanate in the form of 2,4'-, 2,2'- and 4,4'-isomers and mixtures thereof, mixtures of diphenyl methylene diisocyanate and oligomers thereof.
[0087] In still one embodiment, the at least one isocyanate is the product of the reaction of polyisocyanates (for example, the polyisocyanates exposed above), with components containing hydrogen atoms reactive to isocyanate, which form the polyisocyanates polymeric or so-called prepolymers. The prepolymer can generally be prepared by reacting a polyisocyanate with isocyanate-reactive components, which are typically components containing isocyanate-reactive hydrogen atoms, such as a polyether terminated with hydroxyl (polyether polyols), a hydroxyl-terminated polycarbonate or a mixture thereof, and hydroxyl-terminated polyesters (polyester polyol). Non-limiting examples of suitable polyether polyols are preferably polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, preferably an alkyl diol or a polyol having a total of from 2 to 15 carbon atoms, and preferably an alkyl diol or a glycol, which is reacted with an ether, which comprises an alkylene oxide having from 2 to 6 carbon atoms, of a typical ethylene oxide or propylene oxide mode or mixtures thereof, preferably having a functionality of at least 2, for example 2 to 6. The polyether with hydroxyl functionality can be produced primarily by reacting propylene glycol with propylene oxide, followed by the subsequent reaction with ethylene oxide. Primary hydroxyl groups, which result from ethylene oxide, are more reactive than secondary hydroxyl groups, and are therefore preferred. Useful commercial polyether polyols include poly (ethylene glycol), which comprises ethylene oxide reacted with ethylene glycol, poly (tetramethyl glycol) (PTMG), which comprises water reacted with tetrahydrofuran (THF). Polyether polyols may further include the polyamide addition products of an alkylene oxide and may further include, for example, the ethylene diamine addition product, which comprises the reaction product of ethylene diamine and propylene oxide, the product of addition of diethylene triamine comprising the reaction product of diethylene triamine with propylene oxide, and similar polyether polyols of the polyamide type. Copolyethers can also be used in the current invention. Typical copolyesters include the reaction product of glycerol and ethylene oxide or glycerol and propylene oxide. The various polyether intermediates have, in general, a numerical average molecular weight (Mn), as determined by testing the terminal functional groups, which is an average molecular weight, from about 200 to about 10,000, desirably from about 200 to about 5000, and preferably from about 200 to about 3000. In still other embodiments, polyether polyols are a polyether polyol of the EO type . Suitable polyether polyethers of the EO type comprise a polyether polyol having an I- [R- (CH2CH2O) pH] x structure, where x is an integer equal to or greater than 1, p is a number, ranging from 1 to 100, I is an initiator and R represents a series of epoxides, the pH (CH2CH2O) groups being linked to R via an ether bond. The initiator I can be an alcohol, an amine, a polyalcohol, a polyamine, or a component, which comprises one or more alcohol groups and one or more amine groups.
[0088] In still a preferred embodiment, the isocyanate comprises MDI. Preferably, MDI is in the form of its 2,4'-, 2,2'- and 4,4'-isomers and mixtures thereof, or in the form of mixtures of diphenyl diisocyanates methane (MDI) and oligomers thereof, or in the form of mixtures of these diphenyl methane diisocyanates (MDI) and oligomers thereof. In some modalities, MDI is in the form of its 2,4'-isomer, or in the form of mixtures of the 2,4'-isomer and its oligomers. The use of isocyanates containing 2,4'-MDI partially inhibits crosslinking between two cellulosic chains, compared to the use of pure 4,4'-MDI, which results in more crosslinking. In this way, by choosing the type of initial MDI, the amount of pending isocyanates and the extent of the crosslinking can be dimensioned. Preferably, the at least one isocyanate is a mixture of 2,4'- or 4,4'-MDI. In still some embodiments, the polyisocyanate comprises a polymeric polyisocyanate. In still some embodiments, the polyisocyanate comprises a polymeric polyisocyanate of high functionality, with a functionality of at least 2.5, and preferably of at least 2.7. As used herein, q Vgtoq “fupekqpcnkfcfg” tgfgtg is the average number of isocyanate groups per molecule, on average, relative to a statistically relevant number of molecules present in the isocyanate.
[0089] In still some embodiments, the at least one isocyanate comprises a polymeric diphenyl methylene diisocyanate.
[0090] Polymeric diphenyl methylene diisocyanate can be any mixture of pure diphenyl diisocyanate 2,4'-, 2,2'-, and 4,4'-methylene) and the superior homologues thereof.
[0091] The polysaccharide derivative, obtained through the process of the present invention, can be used in fillers, fibers, packaging, films, foams, composites, adhesives, coatings, textiles, sealants, rheology modifiers, inks, chromatographic compaction (phase solid), etc. For example, the polysaccharide derivative can still be used in fillers (such as granules), fibers, or textiles.
[0092] In still a preferred embodiment, the polysaccharide derivative is in the form of granules, in which the granules have a particle size distribution, in which the D50 is at most 1.0 mm, and a preferred mode of a maximum of 200 microns, and even more preferred of a maximum of 100 microns, and in an even more preferred embodiment of a maximum of 50 microns, where D50 is further defined as the particle size , in which fifty percent by weight of the particles are smaller than the D50. For example, the D50 (and / or D90 or D95) can be measured by sieving, by measuring the BET surface, or by laser diffraction analysis, for example according to the standard 13320: 2009.
[0093] In still a preferred embodiment, the polysaccharide derivative is in the form of a fiber yarn, with a linear mass density of at most 2,000 denier, and preferably between 5 and 2,000 denier, and more preferably between 5 and 500 denier, and in the most preferred embodiment between 5 and 200 denier.
[0094] In still a preferred embodiment, the polysaccharide derivative is in the form of a textile or a fabric, in which the textile or fabric can be braided or not braided.
[0095] The crystallinity of the polysaccharide derivative, as measured by XRD, is preferably at least 5%. Preferably, the crystallinity of the polysaccharide derivative, as measured by XRD, is at least 10%, preferably at least 20%, and even more preferably at least 30%. The crystallinity index (CI) of the at least one polysaccharide can be at least 10%, for example at least 20%, for example at least 30%, for example at least 40%, preferably at least at least 50%, and preferably at least 60%, for example at least 70%, for example at least 80%.
[0096] In still one embodiment, the at least one polysaccharide is cellulose and the crystallinity of the polysaccharide derivative, as measured by XRD, is at least 10%, preferably at least 20%, and more preferably at least 30%, and preferably at least 40%, more preferably at least 50%, and preferably at least 60%.
[0097] In still one embodiment, the at least one polysaccharide is a starch and the crystallinity of the polysaccharide derivative, as measured by XRD, is at least 5%, preferably at least 10%, more preferably at least 15%, and more preferably at least 20%.
[0098] In still some embodiments, the crystallinity index of the polysaccharide derivative is at least 50%, that of at least one polysaccharide, preferably at least 60%, preferably at least 70%, and an even more preferred method of at least 80%.
[0099] The polysaccharide derivative obtained through the process of the present invention, can be further reacted in a prepolymer. The prepolymer can generally be prepared by reacting the polysaccharide derivative with isocyanate-reactive components, which are typically components containing isocyanate-reactive hydrogen atoms, such as hydroxyl-terminated polyether ( polyether polyols), a hydroxyl-terminated polycarbonate or a mixture thereof, and hydroxyl-terminated polyesters (polyester polyol). EXAMPLES
[00100] The examples described below illustrate the properties of the processes and the polysaccharide derivatives according to the modalities of the present invention. Unless otherwise stated, all parts and percentages in the examples that follow, as well as throughout the report, are parts by weight or weight percentages, respectively. Methods
[00101] The following methods were used in the examples.
[00102] FT-IR analysis (in an ATR mode) was used to identify the urethane stretch modes and isocyanate stretch modes.
[00103] The NCO content of the polysaccharide derivative was determined by titration, according to DIN 53185.
[00104] The crystallinity index (CI) was measured through XRD analysis, as described below: the crystallinity index was measured through X-ray diffraction, using EwMg radiation generated at 45 kV and 36 bad. EwMg radiation consists of components of Mg3 "* 2,37628" po + g "fg" Mg4 "(0.15444 nm).
[00105] For the cellulose-based derivative of Example 1 (and comparative examples 2-3), the CI was calculated from the height ratio between the intensity of the crystalline peak (I002 - AMI) and the total intensity (I002) after subtracting the reference signal, measured without cellulose. The X-ray diffraction spectrum of Avicel PH-101 is provided in Figure 1.
[00106] For the starch-based derivative of example 4 (and comparative example 5), crystallinity was quantified by adjusting a smooth curve, under the main minimum of diffractograms (see line i). The area above the smooth curve was taken to correspond to the crystalline portion. The ratio of the upper area to the total diffraction area was taken as the degree of crystallinity. The X-ray diffraction spectrum of starch is provided in Figure 2. Example 1
[00107] Microcrystalline cellulose (Avicel®) was dried under vacuum at 60 ° C for a period of 12 hours, and then weighed inside a reaction flask. Anhydrous dimethyl sulfoxide (DMSO) was then added and the mixture (20% by weight of crystalline cellulose) was stirred at room temperature for 1 hour. Isocyanate (a mixture of 50% 4,4'-MDI and 50% 2,4'-MDI) was then added to the reaction flask, while under a blanket of nitrogen and stirred vigorously at room temperature ( 1.05 mol of MDI per mol of OH) for 1 hour. The polysaccharide derivative was then filtered and washed with dry acetonitrile. The polysaccharide derivative was then dried under vacuum and filled into the containers swept with nitrogen.
[00108] The FT-IR analysis of the derivative showed a stretch of urethane at 1730 cm-1 and an isocyanate stretch at 2275 cm-1.
[00109] The content of the polysaccharide derivative was NCOv = 1.7 +/- 0.1% by weight.
[00110] The crystallinity index (IC) of pure microcrystalline Avicel® and the polysaccharide derivative were then measured. The cellulose IC was 85% and the polysaccharide derivative IC, prepared in this example, was 82%. This shows that this process for the preparation of the polysaccharide derivative had limited effects on the crystallinity of the mass and the related mass properties of the polysaccharide. Comparative Example 2
[00111] Microcrystalline cellulose (Avicel®) was dried under vacuum at 60 ° C for 12 hours and then dosed inside a reaction flask. Isocyanate (a mixture of 50% 4,4'-MDI and 50% 2,4'-MDI) was added to the reaction flask, while under a blanket with nitrogen and vigorous stirring, at room temperature (1 , 05 mol of MDI per mol of OH) for 1 hour. The material was then filtered and washed with dry acetonitrile. The material was then vacuum dried and filled into nitrogen-swept containers.
[00112] The content of NCO was NCOv = 0.1% by weight. FT-IR analysis (in ATR mode) showed a spectrum identical to the reference cellulose spectrum, showing that cellulose had not been derived with the comparative example process. Comparative Example 3
[00113] Microcrystalline cellulose (Avicel®) was dried under vacuum, at 60 ° C, for 12 hours, and then dosed inside a reaction flask. A 1 wt% solution of microcrystalline cellulose was then produced by adding 4 wt% lithium chloride in 1,3-dimethyl-2-imidazolidinone to the reaction flask, and heating the mixture for 1 hour at 140 ° C, while under nitrogen cover and vigorous stirring. After dissolution, the mixture was then allowed to cool to room temperature. Isocyanate (a mixture of 50% 4,4'-MDI and 50% 2,4'-MDI) was then added to the reaction flask, while under a blanket with nitrogen and vigorous stirring (1,05 mol of MDI per mol of OH).
[00114] The reaction mixture was turned into gel instantly, and provided a brittle material. The material was then washed with dry acetonitrile. The material was then vacuum dried and filled into nitrogen-swept containers. The analysis of the material by XRD indicated a complete amorphous structure, without any residual crystalline signs (CI = 0%). Example 4
[00115] Corn starch (Sigma-Aldrich) was dried under vacuum at 80 ° C for 6 hours and was then dosed into a reaction flask. Anhydrous DMSO was then added and the mixture (10% by weight of corn starch) was then stirred at room temperature for 1 hour. Isocyanate (a mixture of 50% 4,4'-MFI and 50% 2,4'-MDI) was then added to the reaction flask, while under a blanket with nitrogen and vigorous stirring at room temperature (1.05 mol of MDI per mol of OH) for 1 hour. The polysaccharide derivative was then filtered and washed with dry acetonitrile. The material was then vacuum dried and filled into nitrogen-swept containers.
[00116] FT-IR analysis of the polysaccharide derivative showed a 1730 cm-1 urethane stretch and a 2,275 cm-1 isocyanate stretch.
[00117] The crystallinity index (IC) of pure semicrystalline corn starch from the polysaccharide derivative was then measured. The IC of semicrystalline corn starch was 30%, and after modification, the IC was 30%. This shows that this process for the preparation of the starch derivative had limited effects on the crystallinity of the dough and the related dough properties of corn starch. Comparative Example 5
[00118] The corn starch was dried, under vacuum, at 80 ° C, for 6 hours, and then dosed inside a reaction flask. A 10% by weight solution of corn starch was then produced by adding DMSO to the reaction flask, and then heating the mixture at 75 ° C for 1 hour while under a blanket of nitrogen and vigorous stirring. . This solution was then added to isocyanate (a mixture of 50% 4,4'-MDI and 50% 2,4'-MDI), while under a blanket with nitrogen and vigorous stirring at room temperature (1 mol of MDI per mol of OH). The starch was then filtered, and washed with dry acetonitrile. The material was then vacuum dried and filled into nitrogen-swept containers. The XRD analysis indicated a complex amorphous structure, without any residual crystalline signals (CI = 0%).
[00119] FT-IR analysis of the polysaccharide derivative showed a stretch at 1,730 cm-1 and an isocyanate stretch at 2275 cm-1. Comparative Example 6
[00120] D-glucose was dried under vacuum, at 60 ° C, for 12 hours, and then dosed inside a reaction flask. 4,4'-MDI (1,05 mol of MDI per mol of OH) was then added to the inside of the reaction flask, while under blanket with nitrogen, and the mixture was then heated to 200 ° C for 2 hours. After that, the mixture was allowed to cool slowly, at room temperature, over a period of 12 hours. The resulting material was then ground to a fine powder, dispersed in dry Kbr and the IR was then recorded (mode of transmission).
[00121] IR demonstrated a high consumption of NCO functionality (loss of absorption range at 2,275 cm-1). However, no urethane peak at 1,730 cm-1 was observed, indicating that the loss of NCO is not due to the reaction with glycosidic OH groups. However, urea formation is observed. Heat and MDI provided a condensation by glucose dehydration, generating cellobiose, and the released water was then reacted with the MDI to generate urea. Application examples
[00122] The following examples demonstrate that the polysaccharide derivatives, prepared according to the invention, are much more compatible with the polyurethane (PU) components, when dispersed. In addition, it is shown that the retention of crystallinity provides improved properties to the PU system. Example 7
[00123] The polysaccharide derivative prepared in Example 1 was dispersed in SUPRASEC S2020 (MDI enriched with uretonimine), providing a 10% dispersion, by weight, by mixing with a blade under high shear (3,000 rpm, 4 hours). A stable dispersion was then observed, showing no sedimentation observable after 24 hours. Comparative Example 8
[00124] Microcrystalline cellulose (Neat Avicel) was dispersed in SUPRASEC S2020 (MDI enriched with uretonimine), providing a dispersion at 10%, by weight,
[00125] Through mixing under high shear (3,000 rpm, 4 hours). The dispersion showed poor stability, and complete sedimentation was then observed after 2 hours. Example 9
[00126] The polysaccharide derivative prepared in Example 1 was then dispersed in SUPRASEC S2144 (MDI prepolymer), providing a 10% dispersion, by weight, by mixing under high shear (3000 rpm, 4 hours). The material was then poured into a mold and cured by humidity, at room temperature, for 2 days. The tensile strength was then measured from dog bones, at 50 mm / min, at room temperature, according to DIN 53504. The results are shown in Table 1.
Example 10
[00127] The polysaccharide derivative prepared in Example 4 and Comparative Example 5 (Comparative Example 5) was dispersed in SUPRASEC S2144 (MDI prepolymer), providing a dispersion at 10% by weight by mixing with a slide under high shear (3000 rpm, 4 hours). The materials were then poured into a mold and cured by humidity, at room temperature, for 2 days. The tensile strength was measured in dog bones, at 50 mm / min, at room temperature, according to DIN 53504. The results are shown in Table 2.

[00128] These results demonstrate that both isocyanate derivation and crystallinity are important requirements for the derived polysaccharide to provide improved properties.
[00129] It should also be understood that although the preferred modalities have been discussed for the provision of modalities according to the present invention, several modifications or alterations can still be introduced, without departing from the scope and spirit of this invention.

权利要求:
Claims (15)
[0001]
1. Process for the preparation of a polysaccharide derivative, characterized by the fact that it comprises the stages of: (a) contacting at least one polysaccharide excluding cyclodextrin, with at least one non-reactive isocyanate polysaccharide swelling agent in an amount of hair minus 25% by weight based on the total weight of the combined polysaccharide and swelling agent, essentially in the absence of water, at a temperature of 15 to 35 ° C; and (b) subsequently contacting the product from stage (a) with at least one aromatic polyisocyanate; thereby preparing a polysaccharide derivative.
[0002]
2. Process according to claim 1, characterized by the fact that said swelling agent is selected from the group, which comprises sulfoxides, formamides, acetamides, pyrrolidones, pyridines, imidazoles and mixtures thereof.
[0003]
Process according to any one of the preceding claims, characterized by the fact that the at least one polysaccharide comprises at least one glucose subunit.
[0004]
4. Process according to any one of the preceding claims, characterized by the fact that the at least one polysaccharide is selected from the group, which comprises: cellulosic compounds; starches, agarose; alginic acid; alguronic acid; alpha glucan; amylose; amylopectin; arabinoxylan; beta-glucan; callose; capsulane; carrageenan; cellodextrin; cellulin; chitin; chitosan; chrysolaminarine; curdlan; DEAE- sepharose; dextran; dextrin; alpha-cycloedextrin; ficol; fructan; fucoidan; galactoglucomannan; galactomannan; gellan gum; glucan; glucomannan; glycocalix; glycogen; hemicellulose; hypromellosis; icodextrin; quefirano; laminarin; lentinan; levano; lichenin; maltodextrin; mixed-bonded glucan; mucilage; natural gum; oxidized cellulose; paramilon; pectic acid; pectin; pentaamido; pleurane; polydextrose; polysaccharide peptide; porphyran; pullulan; schizophilan; sepharose; synistgrin; sizofiran; sugammadex; welano gum; xanthan gum; xylan; xyloglucan; zymosan; glycosaminoglycans, such as glycosaminoglycan, chondroitin, chondroitin sulfate, dermatan sulfate; heparan sulfate; heparin, heparinoid, hyaluronan, keratan sulfate; restilane, sodium hyaluronate, and sulodexide; and their mixtures.
[0005]
5. Process according to any one of the preceding claims, characterized by the fact that the at least one polysaccharide is a cellulosic compound, selected from the group, which comprises cellulose, nanocellulose, silk varieties, bacterial cellulose, bamboo fiber, carboxymethyl cellulose, cellodextrin, cellophane, celluloid, cellulose acetate, cellulose acetate phthalate, cellulose triacetate, cellulosome, cotton, croscarmellose sodium, crystallate, ciethylaminoethyl cellulose, dissolved pulp, etulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose , hydroxypropyl cellulose, hypromellose, lyocell, mercerized pulp, methyl cellulose, microbial cellulose, microcrystalline cellulose, modal (textile), nitrocellulose, parksina, peroloid, pulp, paper, rayon, sodium cellulose phosphate, supine, viscose, vulcanized fiber, wood fiber, and mixtures thereof.
[0006]
Process according to any one of claims 1 to 4, characterized by the fact that the at least one polysaccharide is a starch, selected from the group, comprising: corn starch, amylose, acetylated diamide adipate, starch, amylopectin , dextrin, dialdehyde starch, erythronium japonicum, high fructose corn syrup, hydrogenated starch hydrosylate, hydroxyethyl starch, hydroxyl propyl phosphate, maltitol, maltodextrin, maltose, pentaamido, phosphate, corn starch, starch, potato starch, phosphate, starch waxy, waxy potato starch, and mixtures thereof.
[0007]
7. Process according to any one of the preceding claims, characterized by the fact that the NCO content of the polysaccharide derivative is at least 0.2%, as measured according to DIN 53185.
[0008]
8. Process according to any one of the preceding claims, characterized by the fact that the polysaccharide derivative is in the form of granules, in which the granules have a particle size distribution, in which the D50 is at most 1 , 0 mm, where the D50 is defined as the particle size, for which fifty percent by weight of the particles are smaller than the D50, according to the ISO 13320: 2009 standard.
[0009]
Process according to any one of claims 1 to 7, characterized by the fact that the polysaccharide derivative is in the form of a thread or fiber, with a linear mass density of at most 2,000 denier.
[0010]
Process according to any one of claims 1 to 7, characterized by the fact that the polysaccharide derivative is in the form of a textile or a fabric, in which the textile or fabric can be braided or not braided.
[0011]
11. Process according to any one of the preceding claims, characterized by the fact that the at least one swelling agent is selected from the group, comprising: dimethyl sulfoxide, diethyl sulfoxide, methyl methyl sulfoxide, N, N- dimethyl formamide, N, N-diethyl formamide, N, N-ethyl methyl formamide, N-methyl-pyrrolidone, pyridine, bromo-pyridine, chloro-pyridine, N, N-dimethyl acetamide, N, N-diethyl acetamide, N, N-ethyl methyl acetamide, 1,3-dimethyl-2-imidazolidinone, imidazolidinone, 1-methyl-2-imidazolidinone, 1-ethyl-2-imidazolidinone, 1-allyl-3-methyl imidazolium chloride, 1-butyl chloride -3- imidazolium, 1-ethyl-3-methyl imidazolium chloride, and mixtures thereof.
[0012]
12. Process according to any of the preceding claims, characterized by the fact that stage (a) is carried out for a period of time of at least 30 minutes, before stage (b).
[0013]
13. Process according to any one of the preceding claims, characterized by the fact that the water content in at least one polysaccharide, at least one aromatic polyisocyanate and at least one swelling agent is, at most, 0, 5% by weight.
[0014]
14. Process according to any one of the preceding claims, characterized by the fact that it comprises one or more additional stages, such as washing stages, drying stages, or unloading stages.
[0015]
15. Polysaccharide derivative, characterized by the fact that it is obtainable through the process as defined in any of the preceding claims.

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同族专利:

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公开号 | 公开日

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RU2015103729A|2016-08-27|

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RU2633583C2|2017-10-13|

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US9815911B2|2017-11-14|

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US20150152196A1|2015-06-04|

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EP2682408A1|2014-01-08|

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CA2874285A1|2014-01-09|

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EP2870181A1|2015-05-13|

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CN104640883B|2019-03-26|

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WO2014005779A1|2014-01-09|

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IN2014DN09973A|2015-08-14|

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EP2870181B1|2018-08-08|

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CN104640883A|2015-05-20|

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PL2870181T3|2018-12-31|

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BR112014032147A2|2017-06-27|

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CA2874285C|2020-03-24|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-12-08| B09A| Decision: intention to grant|

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2020-12-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/06/2013, 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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EP12175126.7|2012-07-05|

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EP12175126.7A|EP2682408A1|2012-07-05|2012-07-05|Derivatized Polysaccharide|

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PCT/EP2013/061543|WO2014005779A1|2012-07-05|2013-06-05|Process for preparing derivatized polysaccharides|

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