法国专利FR3023555A1 PROCESS FOR DEPOLYMERIZING LIGNIN

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专利摘要:
The present invention relates to a process for the depolymerization of lignin and the use of this process in the manufacture of fuels, electronic components, plastic polymers, rubber, medicaments, vitamins, cosmetics, perfumes, products foodstuffs, synthetic yarns and fibers, synthetic leathers, glues, pesticides, fertilizers. It also relates to a process for manufacturing fuels, electronic components, plastic polymers, rubber, medicines, vitamins, cosmetics, perfumes, food products, synthetic yarns and fibers, synthetic leathers, glues , of pesticides, of fertilizers, comprising a lignin depolymerization step by the method according to the invention.
公开号:FR3023555A1
申请号:FR1456637
申请日:2014-07-09
公开日:2016-01-15
发明作者:Elias Feghali；Thibault Cantat
申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
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[0001] The present invention relates to a process for the depolymerization of lignin and the use of this process in the manufacture of fuels, electronic components, plastic polymers, rubber, medicaments, vitamins, cosmetic products. , perfumes, food products, synthetic yarns and fibers, synthetic leathers, glues, pesticides, fertilizers. It also relates to a process for manufacturing fuels, electronic components, plastic polymers, rubber, medicines, vitamins, cosmetics, perfumes, food products, synthetic yarns and fibers, synthetic leathers, glues , of pesticides, of fertilizers, comprising a lignin depolymerization step by the method according to the invention. Wood is composed of three major constituents: cellulose, hemicellulose and lignin. Cellulose and hemicellulose are already valued in industry, especially in the paper industry. This use generates millions of tons of lignin-rich by-products each year that are used as low-heat-rate fuel to provide heat and energy to paper-making processes. In parallel, a minimal amount of the lignin is isolated by direct extraction from plants (F. G. Calvo-Flores and J. A. Dobado, ChemSusChetn, 2010, 3, pages 1227-1235).
[0002] Lignin is the most abundant substance in terms of the source of aromatic groups in nature and the largest contributor to soil organic matter (SY Lin, in Methods in Lignin Chemistry, Springer Series in Wood Science (Ed .: CW Dence ), Springer, Berlin 1992). It results from the radical polymerization of three monomers named monolignols: p-coumarilyl alcohol, coniferyl alcohol, and sinapyl alcohol, which after polymerization by dehydrogenation with peroxidase respectively give the p-hydroxyphenyl residues (H), guaiacyl (G), and syringyl (S) as illustrated in Figure 1 below (R. Vanholme, K. Morreel, J, RW Boerjan, Curr Opin Plant Biol 2008, 1.1, pages 278-285): ## STR1 ## Mono radical polymerization by dehydrogenation with peroxidase. Figure 1. The complexity and the diversity of the structure of lignin is largely dependent on its origin. on plant taxonomy, it has been proposed that lignin from gymnosperms (called "softwood" or "softwood" in English) has more residues G, than that resulting from angiosperms (called "hardwood" or hardwood in English) , which contains a mixture of G and S residues, and the lignin from herbaceous plants contains a mixture of the three aromatic residues H, G and S. A more rigorous classification technique was to rely on a chemical approach in which lignins are classified according to the abundance of G, H and S units in the polymer Four major lignin groups have thus been identified: type G, type-GS, type HGS and type HG (FG Calvo-Flores and JA Dobado, ChemSusChem 2010, 3, pages 1227- 1235) Whatever the type of lignin, this biopolymer is characterized by a great chemical heterogeneity and consists of propyl-phenol units linked to one another via various types of C-0 and CC bonds of the type aryl ether, aryl glycerol and 3-aryl ether. Figure 2 shows the structure of lignin proposed by E. Adler, Wood Sei. Teehnol. 1977, 11, page 169.
[0003] The ether linkages represent about two-thirds of the links. More specifically, the bonds of the type 13-0-4 and a-0-4, which are part of the alkylaryl ethers, are the most abundant. Typically, the lignin of angiosperms (hardwood or hardwood in English) contains 60% of type 13-0-4 bonds and 6-8% of type a-0-4, and lignin from gymnosperms (softwood or softwood). in English) contains 46% of type 13-0-4 and 6-8% type a-0-4. Although the proportion of these links varies considerably from one species to another, typical values extracted from M. p.
[0004] Pandey, C. S. Kim, Chem. Eng Technol., 2011, 34, 29, are listed in the table in Figure 3. Softwood or Hardwood or Softwood (spruce) link Hardwood (birch) 11-0-4 46 60 a-0-4 6- 8 6-8 4-0-5 3.5-4 6.5 p-5 9-12 6 5-5 9.5-11 4.5 7 7 P-I3 2 3 Other 13 5 Figure 3 The chemical structures of the bond types the most abundant present in the lignin are shown in Figure 4. ## STR2 ## The most abundant types of lignin linkages Figure 4 Lignin represents the largest renewable pool of available aromatic compounds. Due to its high aromatic content, lignin has great potential to function as an alternative to non-renewable fossil resources for the production of high value-added aromatic chemicals, ie products whose processing is increasing. significantly their commercial value. As high value added aromatic chemicals, for example, 4-propylbenzene-1,2-diol (at $ 3,700 / kg) or 4- (3-hydroxypropyl) -1,2-benzenediol may be mentioned. (at $ 3100 / kg). Thus, the valorization of lignin involves its conversion into valuable and useful aromatic products via its depolymerization. However, because of its amorphous, polymeric, and strongly ether-linked structure, its depolymerization to produce usable molecules is a challenge. In addition, the lignins are structurally very diverse and, depending on the plant source used, they contain different proportions of the three basic monomers (p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol). The development of a process of depolymerization by the cleavage of the ether bonds will thus contribute significantly to the valorization of lignin. However, the direct depolymerization of lignin is difficult because its structure is highly functionalized and branched and its steric hindrance can limit the access of the catalyst to the active sites. On the other hand, the chemical heterogeneity of lignin which is due to the presence of several residues G, H, S present at variable rates depending on the nature of the plant and the presence of various types of C-0 bonds and CC-type aryl ether, aryl glycerol and P-aryl ether, complicates the production of pure chemicals during the transformation of lignin. Given the difficulty of direct lignin depolymerization, scientists synthesized chemically pure models, representative of ethylene linkages present in lignin, to study their reactivity (I Zakzeski, P. C. A.
[0005] Bruijnincx, A. L. Jongerius and B. M. Weckhuysen, Chem Rev., 2010, 110, page 3552). The majority of lignin depolymerization studies have focused on these models and have not been implemented on the complex structure of naturally occurring lignins. Examples of cleavage of C-O bonds of the 3-O-4 motif on lignin models using redox or reductive catalysis are given below. - Bergman, Ellman et al. (J.M. Nichols, L.M. Bishop, R.G. Bergman, J.A.A. Ellman, J. Am.Chem.Soc.Publ., 2010, 132, pages 12554-12555) have developed a ruthenium catalyzed covalent redox cleavage reaction. The 3-0-4 patterns of lignin were cleaved with isolated yields ranging from 62 to 98%. The reaction is carried out according to a tandem mechanism of dehydrogenation of the α-alcohol followed by a reducing cleavage of the aryl ether. On the other hand, James et al. (A. Wu, Patrick BO, Chung E. & James BR, Dalton Trans., 2012, 41, page 11093) have shown that a ruthenium complex is capable of catalyzing the direct hydrogenolysis of the ketone equivalent of the 0-unit. -0-4 with hydrogen gas. However, the authors observed that models of the 13-0-4 motif containing the y-OH function, were not reactive. Recently, Leitner et al. (T. vom Stein, T. Weigand, C. Merkens, Jurgen Klankermayer, W. Leitner, ChemCatChem, 2013, 5, pages 439-441) have described a redox cleavage reaction of C-O bonds of the 13-0- 4, through intramolecular hydrogen transfer. This reaction involves a catalyst based on ruthenium (noble and expensive metal), a ligand triphos (ligand also very expensive) and high temperatures (heating at 135 ° C). In addition, depending on the model of the 3-0-4 unit used, the implementation of the reaction may be more or less simple. A vanadium catalyst was used by Toste et al. (S. Son and F. D. Toste, Angew Chem Ed, 2010, 49, pages 3791-3794) for the cleavage of C-O bonds of the 13-0-4 motif and the formation of aryl enones. This redox transformation is carried out in ethyl acetate at 80 ° C. The catalyst load is 10 mol% and after 24 hours the reaction can reach up to 95% conversion of the starting lignin model to aryl enone. As a redox reaction, the products obtained are generally very oxygenated and therefore low in energy. More recently, the same group (M. W. Chan, S. Baller, H. Sorek, S.
[0006] Sreekumar, K. Wang, F.D. Toste, ACS Cotai., 2013, 3, pages 1369-1377) has demonstrated the applicability of this redox cleavage process to the degradation of lignin extracted from Miscanthus giganteus (elephant grass). The results of the GPC and 2D NMR studies of the degradation of lignin dioxasolv and acetosolv resembled the data obtained with the lignin models, which confirms the selectivity of the process for the 13-0-4 bonds. By the way, only the Miscanthus giganteus, which is a grass, was tried and not the wood. Finally, the authors were able to identify and quantify, by GC / MS, volatile phenolic compounds (such as vanillin, vanillic acid, syringic acid and syringaldehyde) produced in the reaction. Nevertheless, no pure chemical could be isolated from this process and partially characterized mixtures were obtained. In 2011, a selective process for the hydrogenolysis of aromatic C-O bonds in alkylaryl ethers and diaryl ethers was developed by Sergeev and Hartwig (A. G. Sergeev and J.F. Hartwig, Science, 2011, 332, page 439). This process allows the selective formation of arenes and alcohols from lignin models and by using a soluble nickel-carbene complex. The reaction is carried out in ni-xylene under 1 bar of hydrogen and at temperatures ranging from 80 to 120 ° C. The use of this method allows the cleavage of 4-0-5 (diaryl ether) linkage patterns, to give anisole, benzene, and phenols with moderate yields. Similarly, hydrogenolysis of the lignin α-O-4 unit patterns at 80 ° C under 1 bar of hydrogen gives 3,4 dimethoxytoluene and 2-methoxyphenol in almost quantitative yields. Cleavage of the 13-0-4 model under basic conditions occurs without the presence of catalyst and provides guaiacol at 89% yield but mixed with many other products. The groups of Toste, Ellman and Hartwig have grouped their results on the reduction of lignin and its models in homogeneous catalysis in international application WO2011003029. The precursors used are derivatives of vanadium, ruthenium and rhodium. Only the vanadium and ruthenium complexes were used for the redox depolymerization of lignin extracted from Miseanthus giganteus. Nevertheless, no pure chemical could be isolated by this method and partially characterized mixtures were obtained. - In 2009, Ragauskas et al. (M. Nagy, David K., G. J. P. Britovsek and A. J.
[0007] Ragauskas, Holzforschung, 2009, 63, p. 513) have successfully depolymerized lignin ethanol organosolv (EOL) (ethanol soluble) from pine under reducing conditions. In this study, conventional heterogeneous catalysts as well as novel homogeneous catalysts were employed for cleavage of diaryl ether and dialkyl ether linkages.
[0008] Using the hydrogenolysis conditions: MPa 1-12; 175 ° C; 20 hours, the ruthenium catalyst effectively increases the solubility of lignin (solubility up to 96%) and contributes to its degradation. A decrease in the order of 10% to 20% of the weight average molecular weight (Mw) was obtained (Mw = 1900-2100 g / mol), which corresponds to a polymerization degree (DP) of 10 to 11 monomer units (LB Davin, LB, Lewis NG, Curr Opin Biotechnol., 2005, 16, pages 407-415). On the other hand, according to the authors, the hydrogenolysis of the diaryl ether and alkylaryl ether groups is accompanied by a simultaneous hydrogenation reaction of the aromatic ring. Finally, the identification as well as the detailed formation of the reaction products and the cleavage pathways have not been elucidated. In 2013, the first organocatalytic reduction of lignin model compounds was described by Féghali and Cantat (E. Feghali, T. Cantat, Chem.Commun., 2014, 50, pages 862-865). The latter have shown that B (C6F5) 3 is an effective and selective hydrosilylation catalyst for the reductive cleavage of alkylaryl ether bonds and in particular α-O-4 and 13-O-4 pattern models. In addition, the reduction is carried out under mild conditions (room temperature of 2 to 16 hours), and can be conducted with an inexpensive air stable hydride source such as polymethylhydrosiloxane (PMHS) and tetramethyldisilazane (TMDS). ). Nevertheless, this process could not be extrapolated to the direct depolymerization of lignin. Given the complex, heterogeneous and highly congested polymer structure of lignin which complicates its depolymerization, the depolymerization processes developed in the literature and described above are generally carried out under stringent conditions of temperature and pressure and metals in high catalytic amounts. Moreover, these processes have been developed on chemically pure models, and few have been extrapolated to lignin reduction. In fact, only the processes of Ragauskas et al. (M. Nagy, K. David, G. J. P. Britovsek and A. J. Ragauskas, Holzforschung, 2009, 63, page 513) and Toste et al. (S. Son and F. D. Toste, Angew Chem Int.Ed. 2010, 49, pages 3791-3794) could be extrapolated to lignin. Other processes did not work with lignin. The presence of several impurities, including water, oxygen (02), sulfur molecules, phosphorus molecules and sugar residues can deactivate the catalyst. These impurities can come from, for example, lignocellulose or the process of extracting lignin from lignocellulose. There is therefore a real need for a process for the depolymerization of lignin and overcoming the disadvantages of the prior art.
[0009] In particular, there is a real need for a process for the depolymerization of lignin, said process: - having a high efficiency resulting in a large conversion of lignin into molecules of smaller sizes containing 1 to 2 aromatic rings, and a high selectivity towards certain links of the; to generate aromatic molecules with high added values, in particular molecules containing 1 to 2 aromatic rings; - simple to implement; - Can be implemented under mild and industrially interesting operating conditions. The present invention is specifically intended to meet these needs by providing a process for the depolymerization of lignin into molecules containing from 1 to 2 aromatic rings, by selective cleavage of the sp3-oxygen carbon bond of the alkylaryl ethers present in the lignin, characterized in that, in the presence of a catalyst, a lignin with a sulfur content of less than 1.5% by weight, based on the total mass of the lignin, is reacted with a silane compound of formula (I) (I) wherein R2 and R3 independently of one another are hydrogen, halogen, hydroxyl, alkyl, alkenyl, alkynyl, an alkoxy group, an aryloxy group, a silyl group, a siloxy group, an aryl group, an amino group, said alkyl, alkenyl, alkynyl, alkoxy, silyl, siloxy, aryl and amino groups being optionally substituted, or - R3 is such as defined above and RI and R2 taken together with the silicon atom to which they are bonded form an optionally substituted silylated heterocycle.
[0010] The process for the depolymerization of lignin according to the invention is highly selective with respect to the sp3-oxygen carbon bonds of the alkylaryl ethers present in the lignin and thus essentially targets the sp3-oxygen carbon bonds of the 3-o-4 type, a-0-4, [3-5, 13-13. Without wishing to be bound by the theory, the cleavage of the sp3-oxygen carbon bonds at the 3-o-4, α-O-4 and 3-13 bonds leads to both the depolymerization of lignin and the modification of its structure, whereas the cleavage of the sp3-oxygen carbon bonds at the level of the j3-5 and 13-1 bonds, leads to the modification of the lignin structure without the cutting of the bond between two successive monomeric units .
[0011] The sp2-oxygen carbon bonds of the aryl ethers present in the lignin (essentially the bonds of the 5-5 and 4-0-5 type) as well as any other sp2-oxygen carbon bond present in the lignin remain intact during the process of the invention. The process of the invention makes it possible to overcome the drastic temperature and pressure reaction conditions conventionally used in the literature for the depolymerization of lignin. It also makes it possible to reduce costs by using silanes of formula (I) which are stable in the air and inexpensive. The method of the invention has the advantage of allowing the depolymerization of lignin leading to the production of molecules containing 1 to 2 aromatic cycles having a weight average molecular weight of less than 1500 g / mmol for the molecules in silylated form (molecules all of the oxygen atoms are in silylated form), ie a degree of polymerization of less than 3 monomer units, preferably between 1 and 2 monomer units. The aromatic molecules obtained may contain mono-, di- or tri-oxygenated aromatic rings depending on the abundance of G, H and S units in the lignin used. The proportions of the G, H and S motifs depend on the plant species from which lignin originates and its extraction process. The weight average molar mass of the molecules obtained and therefore their degree of polymerization can be determined by any method known to those skilled in the art, in particular by Size Exclusion Chromatography (SEC).
[0012] Moreover, the process of the invention can generate methane and hydrogen (of the order of 7 to 15% by weight of the mass of lignin introduced). These two gases may optionally be used as fuels to supply energy to the process of the invention. In the process of the invention, the silane compounds of formula (I) ensure the cleavage by reduction of the sp3-oxygen carbon bonds of the alkylaryl ethers present in the lignin under catalytic conditions. Aromatic molecules containing 1 to 2 aromatic rings having a weight average molecular weight of less than 1500 g / mol for the molecules in silylated form (ie a degree of polymerization of less than 3 monomer units, preferably between 1 and 2 monomer units) are thus obtained with a good productivity (of the order of 20 to 99%, for example), and a very good selectivity vis-à-vis the sp3-oxygen carbon bonds OE-O-4, 13-5, l and pp .
[0013] In the context of the present invention, the yield corresponds to the amount of aromatic molecules containing 1 to 2 aromatic rings, with a weight average molecular weight of less than 1500 g / mol for the molecules in silylated form (ie a degree of polymerization lower than 3 monomer units, preferably between 1 and 2 monomer units) isolated relative to the amount of lignin initially introduced: Productivity = m (aromatic molecules) / m (lignin) m being the mass expressed in gram. For the purposes of the present invention, the term "alkyl" means a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms. As linear or branched saturated alkyl, there may be mentioned, for example, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl and dodecanyl radicals and their branched isomers. As cyclic alkyl, there may be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicylco [2,1,1] hexyl, bicyclo [2,2,1] heptyl radicals. Unsaturated cyclic alkyls include, for example, cyclopentenyl and cyclohexenyl. By "alkenyl" or "alkynyl" is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 2 to 12 carbon atoms comprising at least one double (alkenyl) or a triple bond (alkynyl) . As such, there may be mentioned, for example, ethylenyl, propylenyl, butenyl, pentenyl, hexenyl, acetylenyl, propynyl, butynyl, pentynyl, hexynyl and their branched isomers. The alkyl, alkenyl and alkynyl groups, within the meaning of the invention, may be optionally substituted by one or more hydroxyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (- CN); one or more aryl groups, with the alkoxy and aryl groups as defined in the context of the present invention. The term "aryl" generally refers to a cyclic aromatic substituent having from 6 to 20 carbon atoms. In the context of the invention, the aryl group may be mono- or polycyclic. As an indication, mention may be made of phenyl, benzyl and naphthyl groups. The aryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more "siloxy" groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more several nitro groups (-NO2), one or more nitrile groups (-CN), one or more alkyl groups, with the alkoxy and alkyl groups as defined in the context of the present invention.
[0014] The term "heteroaryl" generally denotes a mono- or polycyclic aromatic substituent comprising from 5 to 10 members, of which at least 2 are carbon atoms, and at least one heteroatom chosen from nitrogen, oxygen, boron and silicon. , phosphorus and sulfur. The heteroaryl group may be mono- or polycyclic. As an indication, there may be mentioned furyl, benzofuranyl, pyrrolyl, indolyl, isoindolyl, azaindolyl, thiophenyl, benzothiophenyl, pyridyl, quinolinyl, isoquinolyl, imidazolyl, benzirnidazolyl, pyrazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl groups. , pyrirnidilyl, pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl. The heteroaryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro (-NO2) groups, one or more nitrile groups (-CN), one or more aryl groups, one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention. The term "alkoxy" means an alkyl, alkenyl and alkynyl group, as defined above, linked by an oxygen atom (-O-alkyl, O-alkenyl, O-alkynyl). The term "aryloxy" means an aryl group as defined above, linked by an oxygen atom (-O-aryl). The term "heterocycle" generally refers to a saturated or initiated 5- to 10-membered mono- or polycyclic substituent containing from 1 to 4 hetero-atoms chosen independently of one another from nitrogen, oxygen, boron, silicon, phosphorus and sulfur. As an indication, mention may be made of morpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, tetrahydrofuranyl, tetrahydropyranyl, thianyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl and isothiazolidinyl substituents. The heterocycle may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more aryl groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more groups. nitro (-NO2), one or more nitrile groups (-CN), one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention. By halogen atom is meant an atom chosen from fluorine, chlorine, bromine and iodine atoms.
[0015] By "silyl group" is meant a group of formula [-Si (X) 31 in which each X, independently of one another, is selected from a hydrogen atom; one or more halogen atoms selected from fluorine, chlorine, bromine or iodine atoms; one or more alkyl groups; one or more alkoxy groups; one or more aryl groups; one or more siloxy groups; with the alkyl, alkoxy, aryl and siloxy groups as defined in the context of the present invention. When at least one of X represents several siloxy groups, said siloxy groups may be repeated several times so as to yield polymeric organosilanes of general formula (O Si X 0 Si (X) 3 (X) 3 Si in which X is as defined above and n is an integer between 1 and 20000, advantageously between 1 and 5000, more advantageously between 1 and 1000. In this respect, mention may be made, for example, of polydimethylsiloxane (PDMS), polymethylhydroxysiloxane (PMHS) and tetramethyldisiloxane (TMDS) By "siloxy" group is meant a silylated group, as defined above, linked by an oxygen atom (-O-Si (X) 3) with X such that defined above.
[0016] Within the meaning of the invention, the term "silylated heterocycle" means a mono- or polycyclic substituent, comprising 5 to 15 members, saturated or introduced, containing at least one silicon atom and optionally at least one other heteroatom chosen from nitrogen, oxygen and sulfur. Said silylated heterocycle may be optionally substituted by one or more hydroxyl groups; one or more alkyl groups, one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more aryl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention. Among the silylated heterocycles, there may be mentioned, for example, 1-silacyclo-3-pentene or 1-methyl-1,1-dihydrido-2,3,4,5-tetraphenyl-1-silacyclopentadiene, according to the formulas of Figure 5
[0017] For example, methyl siloxane, 1-methyl-3-pentene-1-methyl-1-hydrido-2,3,4,5-tetraphenyl-1-silacyclopentadiene can be mentioned. phenyl-1-silacyclohexane, 1-iso-bicyclo [2.2.1 heptane, 1-methyl-1-silacyclopentane, 9,9-dihydro-5-silafluorene corresponding to the formulas of FIG. The term "polyol" is understood to mean an organic compound, characterized in that it is an organic compound, characterized in that it contains an organic compound, characterized in that by the presence of a number of hydroxyl groups (-OH) In the context of this invention a polyol compound contains at least one hydroxyl group.To do this, the term polyol means a compound of formula Z- (OH) 0 wherein n is greater than or equal to 1, and Z is selected from one or more alkyl groups, one or more alkoxy groups, one or more siloxy groups, one or more aryl groups, one or more heteroaryl with the alkyl, alkoxy and aryl groups as defined in the context of the present invention. By "amino" group is meant a group of the formula -NR4R5, in which R4 and R5 independently of one another represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocycle, a silyl group, a siloxy group, with the alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, silyl and siloxy groups, as defined within the scope of the present invention; or R4 and R5 taken together with the nitrogen atom to which they are attached form a heterocycle optionally substituted with one or more hydroxyl groups; one or more alkyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (-CN); one or more aryl groups; with the alkyl, alkoxy and aryl groups as defined in the context of the present invention. By "wood" is meant a plant tissue which corresponds to the secondary xylem in plants. The term wood includes all the secondary tissues forming the trunks, branches and roots of woody plants. By "lignin" is meant a biopolymer present in all plants and mainly in vascular plants, woody plants, herbaceous plants and algae. Lignin is one of the main components of wood. Lignin is a polyol rich in aryl groups as defined above. It comes from a plant tissue including leaves, herbaceous stems and woody stems. Depending on its extraction process and its origin, the lignin may contain other chemical groups such as, for example, alkenes, alkynes, secondary and tertiary primary alcohols, ketones, carboxylic acids, acetals, hemiacetals, enols, ethers, esters, allyl alcohols, homoallyl alcohols, nitriles, imines, secondary and tertiary primary amines, amides, halogens, sulfides, thiols, sulfonates, sulfones , sulfates, sulfoxides. For the purposes of the invention, the process for extracting lignin denotes any physical and chemical technique making it possible to extract, isolate, separate and prepare lignin. By way of example, mention may be made of the kraft process (producing kraft lignin), the sulphite process (producing lignosulphonates), the organosolv processes which correspond to the processes using one or more organic solvents for extracting lignin (L e processes : Acetocell, Alcell, Acetosolv, ASAM, Organocell, Milox, Formacell, Batelle / Geneva phenol), the Steam-explosion process, the Klason process, the sodaAQ process (producing lignin soda or alkaline lignin), the extraction process biology of lignin by biological organisms such as bacteria and enzymes, and the process of extracting lignin by acid hydrolysis. The organosolv processes are described by the following references: a) Alcell: J. H. Lora, W. G. Glasser, J Polym Environ, 2002, 10, 39-48; (b) Acetocell: Bojan Jankovic, Bioresource Technol., 2011, 102, 9763-9771; c) Acetosolv: J. C. Parajo, J. L. Alonso, D. Vazquez, Bioresource Technology, 1993, 46, 233-240; d) ASAM: Miranda L, H. Pereira, Holzforschung, 2002, 56, 85-90; e) Batelle / Genevaphenol: A. Johansson, O. Aaltonen, P. Ylinen, Biomass 1987, 13, 45-65, Formacell: X.F. Sun, R.C. Sun, P. Fowler, M.S. Baird, Carbohydr. Polyrn., 2004, 55, 379-391; (g) Milox: P. Ligero, A. Vega, J. J. Villaverde, Bioresource Technol., 2010, 101, 3188-3193; h) Organocell: A. Lindner, G. Wegener, J Wood Chem. Technol. 1988, 8, 323-340. In the context of the invention, the lignin extraction process also includes lignin treatment processes for the purpose of introducing chemical functionalizations, changing the physical properties and / or modifying the average molar mass of the lignin. lignin. Lignin is a polymer formed by a distribution of polymeric fragments having different molar masses. The average molar mass of the lignin therefore corresponds to the average of the masses of these polymeric fragments; it can be calculated with respect to the mass of the fragments or in relation to their numbers. Whatever the process used to extract and / or treat the lignin, it is essential that the lignin obtained be sulfur-free, that is to say that it contains a sulfur content of less than 1.5% by weight. , relative to the total mass of lignin. Indeed, the inventors have observed, quite unexpectedly, that when the lignin contains a sulfur content equal to or greater than 1.5% by weight, relative to the total mass of the lignin, the depolymerization of the lignin by the method of the invention does not take place or it is partial. When the depolymerization is partial, it leads to molecules of average molecular weight by weight greater than 1500 g / mol for the molecules in silylated form. The sulfur content of the lignin used in the process of the invention is therefore advantageously equal to or greater than zero and remains below 1.5% by weight, relative to the total mass of the lignin, as defined herein. below: 0 <lignin sulfur content <1.5% by mass, based on the total mass of the lignin. The level of sulfur can be determined by the physical and chemical techniques known to those skilled in the art, such as, for example, elemental analysis, ion chromatographic assay, infrared spectrophotometry, sulfur oxidation to SO2 and assaying thereof. by techniques known to those skilled in the art, such as, for example, the acidimetric assay, the iodometric assay, the complexometric assay. According to a preferred variant of the invention, in the silane compound of formula (I), R 1, R 2 and R 3 represent, independently of one another, a hydrogen atom, an alkyl group, an alkoxy group, a amino group, an aryl group, a silyl group of formula [-Si (X) 3] with X as defined above with at least one of X representing more than one siloxy group, said siloxy groups may be repeated several times so as to to give polymeric organosilanes having a general formula X (X) 3 SiO SiO Si (X) 3 X in which n is an integer from 1 to 20000, advantageously from 1 to 5000, more preferably from 1 to 1000, alkyl, alkoxy and aryl groups being optionally substituted. More preferably, in the silane compound of formula (1), R1, R2 and R3 independently of one another represent a hydrogen atom; an alkyl group selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers; an alkoxy group whose alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers; an aryl group selected from benzyl and phenyl groups; a silyl group as described above selected from polydimethyl siloxane (PDMS), polymethylhydroxysiloxane (PMHS) and tetrarnethyldisiloxane (TMDS).
[0018] By catalyst, within the meaning of the invention is meant any compound capable of modifying, in particular by increasing, the speed of the chemical reaction in which it participates, and which is regenerated at the end of the reaction. This definition encompasses both catalysts, that is, compounds that exert their catalytic activity without the need for any modification or conversion, and compounds (also called pre-catalysts) that are introduced into the medium. and converted therein to a catalyst. In particular, it is necessary for the catalyst to be chosen taking into account in particular its steric bulk, its ability to activate the silane and its solubility in the reaction medium. In the process of the invention, the catalyst can be a catalyst. organic compound selected from: - carbocations of formula (X1) 3C + with Xl representing a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a silyl group, a siloxy group and a halogen atom, such as defined above, said carbocations being chosen from the trityl cation ((C6H5) 3C +), the tropilium (C7H7) F, the benzyl cation (C6H5CF12 +), the allyl cation (CE13-CH + -CH = CH2), methylium (CH3 +), cyclopropylium (C3H5 '), cyclopropyl carbocation of formula C3H5-C + RIR2 with R1 and R2 as defined above said carbocation being selected from cyclopropyl dimethyl carbocation and dicyclopropyl carbocation, acylium (R1-C) = 0) 'with R1 as defined above and chosen from methyl, propyl and benzyl, the benzenium cation (C6115) +, the norbornyl cation (C7H11) ÷ - the oxoniums chosen from (CH3) 3013F4 (Meerwein salt) and (CH3Cl-12 ) + BF4- a silylium ion (R1) 3Si + with R1 as previously defined, for example, selected from Et3Si + and Me3Si +; disilyl cations, preferably disilyl cations having a bridging hydride chosen from the formulas indicated below. If said disilyl cations can be synthesized by those skilled in the art as described by R. Panisch, M. Boite, and T. Muller, J. Am. Chem. Soc. 2006, 128, pages 9676-9682).
[0019] The carbocations mentioned above are commercial or can easily be synthesized by those skilled in the art by various synthetic methods, for example: the cation pool process, the internal redox process, the method using a leaving group methods using Lewis or Bronsted acids. These methods are described in the following references: R. R. Naredla and D. A. Klumpp, Chem. Rev. 2013, 113, pp. 6905-6948; Mr. Saunders. and H. A. Jirnenez-Vazquez, Chem. Rev. 1991, 91, pages 375-397. It should be noted that the anionic counterion of the silylium ion, carbocations and disilyl cations mentioned above is preferably a halide selected from F-, CL, Br- and I-, or an anion selected from BF4-, SbF6 B (C6F5) 4-, B (C61-15) 4-, TfO- or CF3SO3-, PF6-.
[0020] In the process of the invention, the catalyst can also be organometallic. In this respect, mention may be made of the iridium (RPX2CX2P) Ir (R7) (S) 1 + Y-) complexes of formula (III) + in which - R6 represents an alkyl or aryl group as defined above, and Preferably an iso-butyl group - R7 represents a hydrogen atom or an alkyl group as defined above, and preferably a hydrogen atom; and X 2 represents a group -CH 2 - or an oxygen atom, and preferably an oxygen atom; Y represents a counterion selected from B (C6F5) 4 and B (C6H5) 4, and preferably B (C6F5) 4; S represents a solvent molecule, coordinated with the complex, chosen from dimethylsulfoxide (DMSO), acetonitrile (CH3CN) and acetone (CH3COCH3), and preferably acetone. According to a preferred embodiment of the invention, the iridium catalyst is (POCOP) Ir (H) (acetone)] S (C6F5) 4- with (POCOP) representing 2,6-bis (di-tertbutylphosphinito) This catalyst can be prepared according to the methods described by I. Gottker-Schnetmann, P. White, and M. Brookhart, J. Am, Chem. Soc. 2004, 126, pp. 1804-1811; and J. Yang and M. Brookhart, J. Am. Chem. Soc. 2007, 129, pages 1265620 12657. In the process of the invention, the catalyst can also be organometallic. In this respect, mention may be made of the ruthenium complexes of formula (IV) in which - K represents a hydrogen atom or an alkyl group as defined above, R./2 preferably being a group methyl; - R13 represents an aryl or an alkyl group as defined above, said aryl and alkyl groups being optionally substituted, R13 preferably being pFC6H4; Z represents a group -CH 2 -, an oxygen atom or a sulfur atom, Z preferably being a sulfur atom; and K represents a counterion selected from B (C6F5) 4 - and [CHBI1H5C16] K being preferably B (C6F5) 4- This type of catalyst may be prepared according to the methods described by T. Stahl, HFT Klare, and M Oestreich, J. Am, Chem Soc., 2013, 135, pages 1248-1251 The catalyst may also be of Lewis acid type chosen from organometallic and metal catalysts: boron compounds of formula B (X3) With X3 representing a hydrogen atom, an alkyl group, an aryl group, an alkoxy group as defined above, said boron compounds being chosen from BF3, BF3 (Et20), BC13, BBr3, triphenyl hydroborane, tricyclohexyl; hydroborane, B (C6E5) 3, Bmethoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane (B-benzyl) -9 -BBN) - borenium compounds R1R2B + with R1 and R2 as defined above, said borenium compounds being for example Me-TBD-BBN +, borenium derivatives ferrocene corresponding to the formula borenium ferrocene in which R1 and R3 as defined above, for example, R1 is a phenyl group and R3 is 3,5-dimethylpyridyl; aluminum compounds selected from AlCl3, AlBr3, Al (O-i-Pr) 3 aluminum isopropoxide, aluminum ethanoate (Al (C2H302)), Krossing salt [Ag (CH2Cl2)) 1 {A1fOC (CF3) 314}, Li {Al [OC (CF3) 3] 41, the cationic aluminum compounds of formula (X4) 2A1 + with X4 being a halogen atom, an alkoxy group, an alkyl group as defined above such as, for example, Et2A1F; iridium compounds selected from InCl3, In (OTf) 3; iron compounds selected from FeCl3, Fe (OTf) 3; tin compounds selected from SnC14, Sn (OTf) 2; phosphorus compounds such as PC13, PC15, POC13; trifluoromethanesulfonate or triflate (CF 3 SO 3) compounds of transition metals and lanthanides selected from scandium triflate, ytterbium triflate, yttrium triflate, cerium triflate, samarium triflate, niodinium triflate. In the context of the present invention OTf represents the triflate ion or trifluoromethanesulfonate of formula CF3SO3-: the terms triflate or trifluoromethanesulphonate, OTf or CF3SO3-can therefore be used indifferently to designate the same entity. The preparation of borenium ferrocene derivatives is described by J. Chen, R. A. Lalancettea and F. Jakle, Chem. Commun., 2013, 49, pages 4893-4895); the preparation of Krossing salts is described by I. Krossing, Chem.-Eur. J., 2001, 7, page 490; and the preparation of Et2Ar is described by M. Khandelwal and R. J. Wehmschulte, Angew. Chem. Int, Ed. 2012, 51, pages 7323-7326. According to a preferred variant of the invention, the catalyst is an organometallic catalyst chosen from BF3; InC13; triphenylcarbenium tetrakis (perfluorophenyl) borate [(Ph) 3C413 (C6F5) 4-, B (C6F5) 31.
[0021] Some of the abbreviations used in the context of the invention are represented in FIG. 7: HNN TBD Me-TBD-BBN + R2 carbocation cyclopropyl SiH. "- PhDS Ph Ph Ph cation trityl cation tropylium carbocations norbornyl R cation acylium eSi cation silylium R3 R1 borenium ferrocene Si-OH PMHS Si-H Si 0 Si-H PDMS / Si Si 1-1 0 1-1 TMDS Figure 7 The catalysts may, if appropriate, be immobilized on heterogeneous substrates to ensure separation The said heterogeneous supports may be chosen from supports based on silica gel and on plastic polymers such as, for example, polystyrene, carbon-based supports chosen from carbon nanotubes, and silica carbide. alumina and magnesium chloride (MgCl 2) In the process according to the invention, the reaction can take place under a pressure of one or a mixture of inert gas (s) chosen from nitrogen and argon, or s gases generated by the process including methane and hydrogen. The pressure may be between 0.2 and 50 bar, preferably between 0.2 and 30 bar, more preferably between 1 and 20 bar, inclusive. The temperature of the reaction may be between 0 and 150 ° C, preferably between 0 and 125 ° C, more preferably between 25 and 70 ° C inclusive. The duration of the reaction depends on the conversion rate of the silane compound of formula (I), the nature of the lignin and the desired silylation rate. The reaction may be carried out for a period of 1 minute to 200 hours, preferably 1 minute to 48 hours, preferably 10 minutes to 48 hours inclusive. The process of the invention, in particular the reaction between the different reactants, can take place in a mixture of at least two solvents chosen from: silyl ethers, preferably chosen from 1,1,1,3,3,3-hexamethyldisiloxane ((Me3Si) 20), 1,1,1,3,3,3-hexaethyldisiloxane ((Et3Si) 20). hydrocarbons, preferably chosen from benzene, toluene, pentane and hexane; sulfoxides, preferably chosen from dimethyl sulphoxide (DMSO); alkyl halides, preferably chosen from chloroform, methylene chloride, chlorobenzene and dichlorobenzene.
[0022] The silanes of formula (I) and the catalysts used in the process of the invention are, in general, commercial compounds or can be prepared by methods known to those skilled in the art. The mass ratio between the silane compound of formula (I) and the lignin depends on the type of lignin employed and on the type of final molecules desired (obtaining silyl ethers of the Iib, Iid, Iif type as represented in the examples or obtaining silyl ethers of type IIa, He, bind as shown in the examples). Compounds 11a-11f are therefore silyl ethers which can be deprotected to give the corresponding alcohols of formula (IV) by hydrolysis. The hydrolysis of the silylated ethers can be carried out by chemical hydrolysis techniques (acidic or basic condition) known to those skilled in the art. Enzymatic hydrolysis can also be carried out. Examples of hydrolysis are provided in the exemplary embodiments of the process of the invention.
[0023] Silyl ethers containing a substituted propyl chain of formula IIb, 11d, 11f may also give other silyl ethers containing an unsubstituted propyl chain of the type Ha, He, He by the same method as that used for the depolymerization of lignin. Since the depolymerization process reduces sp3-oxygen carbon bonds, the silylated bonds (-C-O-Si-) can be easily reduced to alkane (-C-H). Obtaining silyl ethers containing an unsubstituted propyl chain will depend on the number of equivalents of silane compound of foimule (1) added. Thus, in the context of the present invention, the mass ratio between the silane compound of formula (I) and lignin may be between 0.5 and 6, preferably between 1 and 4 inclusive.
[0024] The amount of catalyst used in the process of the invention is from 0.001 to 1 equivalent by weight, preferably from 0.001 to 0.9 equivalent by weight, more preferably from 0.01 to 0.9 equivalent by weight, even more preferably From 0.01 to 0.5 weight equivalents, limits included, relative to the initial mass of the As already indicated, the depolymerization of lignin leads to the production of aromatic molecules containing 1 to 2 aromatic rings of average molar mass. by weight less than 1500 g / mol for the molecules in silylated form (ie a degree of polymerization of less than 3 monomer units, preferably between 1 and 2 monomer units). The weight average molar mass of the aromatic compounds and the degree of polymerization of the lignin can be determined by the usual techniques used in this field and known to those skilled in the art such as, for example, size exclusion chromatography. After depolymerization, the resulting aromatic compounds are generally at least partially in silylated form, particularly on the phenolic residues of lignin. However, simple hydrolysis under conditions well known to those skilled in the art leads to the corresponding aromatic compounds in their unsilylated forms. A simple filtration can make it possible to recover the optionally supported catalyst and to eliminate any by-products.
[0025] Thus, the process of the invention allows lignin to become the main source of aromatic compounds of biological origin for the chemical industry. Aromatic compounds with high added values such as, for example, benzene, toluene, xylenes (BTX), substituted coniferols, phenol, aromatic polyols, and quinines can thus be obtained and used in the synthesis of phenol resins. formaldehyde, polyolefin-lignin polymers, polyester-lignin polymers, polyurethanes, bio-plastics, epoxy resins. The aromatic compounds obtained by the process of the invention can therefore be used as raw materials in the construction sector, in perfumes, in the petrochemical, food, electronic, textile, aeronautic, pharmaceutical, cosmetic and agrochemical industries. . The subject of the invention is therefore the use of the process for the depolymerization of lignin according to the invention in the manufacture of fuels, electronic components, plastic polymers, rubber, medicaments, vitamins, cosmetic products, perfumes, food products, synthetic yarns and fibers, synthetic leathers, glues, pesticides, fertilizers. The invention also relates to a process for producing fuels, electronic components, plastic polymers, rubber, medicaments, vitamins, cosmetics, perfumes, food products, yarns and synthetic fibers. , synthetic leathers, glues, pesticides, fertilizer, characterized in that it comprises a lignin depolymerization step by the method according to the invention. In addition to the good productivity and the good selectivity, the process of the invention makes it possible to use lignin, which represents the largest reservoir of aromatic compounds of biological origin, and a mild reducing agent (silane of formula (I )) stable in the air and inexpensive and compatible with the possible presence of functional groups on lignin. The process of the invention allows lignin to become the main source of aromatic compounds of biological origin for the chemical industry. Other advantages and features of the present invention will appear on reading the examples below given for illustrative and non-limiting.
[0026] EXAMPLES The process for the depolymerization of lignin by selective cleavage of the sp3-oxygen carbon bond of the alkylaryl ethers present in the lignin is carried out in the presence of a catalyst, by reacting a lignin with a sulfur content of less than 3% by weight. of lignin, with a silane compound of formula (I) the following experimental protocol. The reagents used, in particular the silane compound of formula (1) and the catalyst are commercial products. General Experimental Protocol for the Depolymerization of Lignin 1. Under an inert atmosphere of argon or nitrogen, the silane compound of formula (1), the catalyst (from 1 to 0.001 mass equivalents calculated with respect to the initial mass of lignin added and half of the amount of solvent are stirred in a glass vessel of suitable volume. The silane concentration in the reaction mixture ranges from 1.0-6.0 mol.L-1 (concentration calculated on the basis of half the final volume of solvent introduced). 2. On the other hand, in a Schlenk tube, the lignin organosolv (10 - 40% equivalent mass of silane added), previously dried overnight with a vacuum ramp, is placed under stirring with the remaining half of the solvent. 3. The solution containing the catalyst and the silane compound of formula (I) is slowly added (addition time 15 minutes-1 hour) with the aid of a syringe and with stirring, to the Schlenk tube. The latter is left open in order to evacuate the gases produced by the reaction. 4, After the end of the addition of the solution and the cessation of the gas evolution, the Schlenk tube is closed and is left stirring. The starting lignin is then soluble almost completely. The reaction monitoring is performed by GC-MS. 5. Once the reaction is complete (reaction time 1 to 72 hours), the solvent and the volatile compounds are evaporated using a vacuum ramp (10-2 mbar). The viscous liquid obtained is purified using silica gel chromatography using an elution gradient of 100: 0 to 0: 100 of pentane: CH 2 Cl 2 for the apolar fractions, and an elution gradient. from 100: 0 to 0: 100 of CH2Cl2: AcOEt for the polar fractions. In the case where a fraction is very polar, the elution can be carried out with a mixture AcOEt: MeOH (50: 50 to 0: 100). It should be noted that depending on the intended application, the purification step may or may not be omitted. 6. Finally, the different fractions from the column are hydrolysed in an acidic medium using 2M HCl or H 2 SO 4 in THF, or in basic medium using NaOH or 30% KOH by weight, or finally with the aid of a fluorinated reagent type: HF-pyridine, TBAF, CsF, NH4F to provide the corresponding hydrolyzed product. A set of results is presented below, giving examples of depolymerization of organosolv lignin. The catalysts tested are B (C6F5) 3 as well as the iridium complex ([(POCOP) Ir (H) (acetone) 1 + 3 (C6F5) 4-), the synthesis of which is described by I. GottkerSchnetmann, P. White, and M. Brookhart, J Am. Chem. Soc. 2004, 126, pp. 1804-1811; and J. Yang and M. Brookhart, J. Am. Chem. Soc. 2007, 129, pages 12656-12657.
[0027] The lignin used is derived from several organosolv (a) Alcell processes: I. H. Lora, W. G. Glasser, J Polym Environ, 2002, 10, pp. 39-48; (b) Acetocell: Bojan Jankovic, Bioresource Technol., 2011,102, pp. 9763-9771; c) Acetosolv: J. C. Parajo, I. L. Alonso, D. Vazquez, Bioresource Technology, 1993, 46, pages 233-240; d) ASAM: I. Miranda, H. Pereira, Holzforschung, 2002, 56, pages 85-90; e) Batelle / Genevaphenol: A. Johansson, O. Aaltonen, P. Ylinen, Biomass 1987, 13, pages 45-65; f) Formacell: X.F. Sun, R.C. Sun, P. Fowler, M.S. Baird, Carbohydr. Polynt, 2004, 55, pages 379-391; (g) Milox: P. Ligero, A. Vega, J. J. Villaverde, Bioresource Technol., 2010, 101, pages 3188-3193; h) Orga.nocell: A. Lindner, G. Wegener, J Wood Chem. Technol. 1988, 8, pages 323-3401 and in particular the AVIDEL process (described by HQ Lam, Y. Le Bigot, M. Delmas, G. Avignon, Industrial Crops and Products, 2001, 14, pages 139-144) which constitutes a optimized version of the Formacell process. The types of wood from which the lignins are derived, are selected with different G / H / S proportions, and a mixture of several types of wood has been used, to show the versatility as well as the robustness of the process. In the context of the invention, the term "robustness of the process" is understood to mean a process which, under very mild operating conditions, allows the cleavage of the chemical functions that are usually very hard to cleave.
[0028] EXAMPLE I: Depolymerization of lignin from platanus (Platanus acerifolia) (extracted by the AVIDEL process) using triethylsilane (Et3SiH) The depolymerization of common plane was carried out following the general depolymerization procedure described above.
[0029] The depolymerization is carried out with 4-5 mol-1 Et 3 SiH as silane (concentration calculated on the basis of half the final volume of solvent introduced). The mass of lignin added corresponds to 30% of the added silane mass and the solvent used is dichloromethane (CH 2 Cl 2). The reaction is carried out in the presence of 20-30% by weight of catalyst (mass calculated with respect to the mass of lignin added). The catalyst used is B (C6F5) 3. The silane and catalyst solution is added over a period of 30 minutes in the Schlenk tube and the reaction is stirred for 24 hours at 25 ° C. After the end of the reaction and the evaporation of the solvent and the volatiles, the viscous liquid obtained is purified using the same conditions as previously described. This liquid consists of a mixture of products of formulas IIa, Hb, He and Id (identified by NMR and by GC-MS). Et3SiO Et3SiO (11a) OSiEt3 Et3SiO OSiEt3 OSiEt3 Et3SiO Et3SiO (11f) The HalIbflic / Hd molar ratio was determined from GC-MS analysis (GCMS-QP2010 Ultra gas chromatograph mass spectrometer equipped with a capillary silica column fissioned: Supelco SLBTm-ms fused silica capillary column (30 mx 0.25 mm x 0.25 lm) as indicated in Table 1. Finally, the fractions resulting from the purification were hydrolysed in an acidic medium using a solution of 2 M HCl in THF After stirring for 16 hours at room temperature (20 ± 5 ° C.), the solvent and the volatiles are evaporated off to give the various corresponding polyols.
[0030] 1H NI (200 MHz, CDCl 3, Me 4 Si) δ (ppm) = 6.71 (1H, d, 3 J = 8.1 Hz, Ar-H), 6.63 (1H, s, Ar-H), 6.58 (1H, s, 1H); H, d, 3J = 8.1 Hz, Ar-H), 2.45 (2H, t, 3J = 7.8Hz, Ar-C), 1.57 (2H, sex, 3J = 7.8Hz, C112-CH3), 0.98 ( 18H, t, 3, / 7.9Hz, CH3CH2Si), 0.90 (3H, t, 3J-7.8Hz, CH3CH2Si), 0.74 (12H, q, 3J = 7.9Hz, CH3CH2Si). 13C NMR (50 MHz, CDCl3, Me4Si): (ppm) -146.5, 144.7, 136.0, 121.3, 120.9, 120.2, 37.4, 24.7, 13.9, 6.9, 5.3, 5.2. HR-MS (APPI): Calculated (M +) (C211-14002Si2), m / z 380.2566; found (M +), m / z 380.2559. Anal. Calculated. for C2fH4002Si2 (molar mass 380.72): C, 66.25; H, 10.59. Found: C, 66.18; H, 10.46. MS: JE (m / z): 380 (9); 351 (4); 207 (8); 117 (4); 116 (11); 115 (100); 88 (7); 87 (74); 59 (45); 58 (4). 1H NMR (200MHz, CDCl3, Me4Si) δ (ppm) = 6.79 - 6.50 (3H, m, Ar-H), 3.60 (2H, t, 3J = 6.6Hz, CH2-O), 2.54 (2H, m.p. H, t, 3 J = 7.6 Hz, Ar-CH 2), 1.79 (2H, quin, 31- 7.0 Hz, Ar-CH 2 -CH 2), 1.05 - 0.88 (27H, m, CH 2 CH 2 Si), 0.84- 0.48 (18H, m.p. H, m, CH 3 CH 2 Si). 13C NMR (50 MHz, CDCl3, Me4Si): δ (ppm) = 146.5, 144.8, 135.4, 121.3, 120.9, 120.3, 62.3, 34.7, 31.5, 6.9, 6.8, 5.2, 5.2, 4.6. MS: 1E (m / z): 87 (100), 115 (57), 59 (38), 89 (28), 207 (24), 32 (16), 235 (11), 88 (10), 337 (9), 511 (8), 116 (6), 86 (6). 11e: 1H NMR (200MHz, CDCl3, Me4Si) δ (ppm) = 6.27 (21.11, s, Ar-I-1), 2.39 (2H, t, 3J = 7.5Hz, Ar-C), 1.69 - 1.45 (2H, m, CH 2 -CH 3), 1.1 - 0.84 (27H, m, CH 3 CH 2 Si), 0.90 - 0.81 (3H, m, CH 3 CH 2 Si), 0.83 - 0.65 (18H, m, CLI 3 CH 2 Si). 13C NMR (50 MHz, CDCl3, Me4Si): δ (ppm) - 147.8, 146.5, 134.5, 113.6, 37.7, 24.6, 13.7, 7.0, 6.8, 5.4, 5.2. Y (m / z): 510 (8); 339 (4); 338 (10); 337 (31); 116 (7); 115 (60); 88 (10); 87 (100); 86 (4); 59 (49). Hd: 111 NMR (200 MHz, CDCl3, Me4Si) (ppm) = -6.28 (2H, s, Ar-H), 3.59 (2H, t = 6.7Hz, CL12-0), 2.48 (2H); , t, 3J = 7.5 Hz, Ar-CH, 2), 1.78 (2H, quin, 3J = 7.3 Hz, Ar-CH 2 -CH 2), 1.13-0.85 (36H, m, CH 3 CH 2 Si), 0.84-0.49 ( 24H, m, CH3CLI2Si). 13C NMR (50 MHz, CDCl3, Me4Si): δ (ppm) = 147.9, 136.6, 134.0, 113.6, 62.3, 34.6, 31.7, 6.9, 6.8, 5.4, 5.2, 4.5.
[0031] MS: JE (nose): 87 (100), 115 (36), 59 (32), 89 (19), 641 (9), 88 (9), 467 (8), 365 (7), 337 (6). ), 642 (5), 640 (5), 116 (4). EXAMPLE 2: Depolymerization of lignin from pine (Pinus pinea) (extracted by the AVIDEL method) using triethylsilane (Et3Sil) The same procedure used for the depolymerization of lignin from common plane tree is used for depolymerization lignin from pine. In this case and after purification, the product Ha is obtained with a very high purity (> 99.7%) with a mass yield of 10 to 20% relative to the mass of lignin employed (non-optimized). This product has been characterized by GC-MS, 13C NMR, 1H NMR and HR-MS. Finally, the hydrolysis of the fractions resulting from the purification is carried out by stirring at 25 ° C. each fraction for 16 h in the presence of a 2 M solution of HCl in THF. Finally, the polyols are obtained after evaporation of the solvent and volatile compounds. EXAMPLE 3: Depolymerization of Lignin from Poplar (Italy) (extracted by the AVIDEL method) using triethylsilane (Et3SiH) The same procedure used for the depolymerization of lignin from common plane tree is used to the depolymerization of lignin from the Poplar of Italy. Similarly, the products obtained in both cases are similar. Among the most volatile products, the formulas Ha and lie are identified by RIVIN and by OC-MS as shown in Table I. EXAMPLE 4: Depolymerization of lignin from birch pendant (Betula pendula) (extracted by AVIDEL method) using triethylsilane (Et3SiH) The same procedure used for the depolymerization of lignin from common plane was used for the depolymerization of lignin from Birch pendant. Similarly, the products obtained in both cases are similar. Among the most volatile products, the products of formulas IIa and IIc are identified by NMR and OC-MS as shown in Table 1. EXAMPLE 5: Depolymerization of lignin from Common Beech (Fagus sylvatica) (extracted by AVIDEL method) using triethylsilane (Et3SiH) The same procedure used for the depolymerization of lignin from common plane was used for the depolymerization of lignin from Common Beech. Similarly, the products obtained in both cases are similar. Among the most volatile products, the products of formulas Ha and He are identified by NMR and by OC-MS as indicated in Table 1. EXAMPLE 6: Depolymerization of the lignin resulting from Eucalyptus (Eucalyptus carnaldulensis) (extracted by the AVIDEL method) using triethylsilane (Et3SiH) The same procedure used for the depolymerization of lignin from Common Beech is used for the depolymerization of lignin from Eucalyptus. Similarly, the products obtained in both cases are similar. Among the most volatile products, the products of formulas IIa, IIb, IIc and IId are identified by NMR and by GC-MS. The IIcilla molar ratio is 76/24 respectively according to GC-MS analysis. EXAMPLE 7 Depolymerization of lignin resulting from Thuya giant (Thuja plicata) (extracted by the AVIDEL process) using triethylsilane (Et3Sill) The same procedure used for the depolymerization of lignin from Eucalyptus (Eucalyptus carnaldulensis), is used for the depolymerization of lignin from giant Thuya. Similarly, the products obtained in both cases are similar. Among the most volatile products, the product of formulas IIa and IIb were identified by NMR and by GC-MS as shown in Table 1. EXAMPLE 8: Depolymerization of lignin from the F315 sawdust mixture (extracted by US Pat. AVIDEL process) using tetramethyldisiloxane (TMDS) The depolymerization of lignin is carried out with the lignin obtained from the mixture of wood F315 (sawdust mixture marketed by the company SPPS extracted from species belonging to the Pinaceae family). In the case where TMDS (tetramethyldisiloxane) is used as silane, there is possibility of gel formation, which makes the reaction very difficult. To do this two solutions can be envisaged: the dilution of the solution 3 to 4 times using CH 2 Cl 2 as a solvent or the use of benzene or toluene as a solvent. However, the reaction will be slower in both cases. If the reaction is carried out in CH 2 Cl 2, the concentration of TMDS is of the order 1-3 mol.L-1 (concentration calculated on the basis of half of the final volume of solvent introduced). 20% by weight of B (C6F5) 3 (calculated mass relative to the mass of lignin added) are required to catalyze the reaction. The mass of lignin added is between 10 to 30% of the added silane mass. The catalyst-silane addition time is 30 to 45 minutes. Then, the reaction is stirred for 24 hours at 25 ° C. After the end of the reaction, the volatile compounds as well as the solvent are evaporated under vacuum (10-2 mbar). The mixture resulting from the depolymerization is degraded during its purification on a silica column and the product obtained is hydrolysed in basic medium, using a mixture of THE and H 2 O containing 10% by weight of NaOH. After stirring for 16 hours at 25 ° C., the volatile compounds and the solvents are evaporated, and the product is purified on a silica column. Hydrolysis of the mixture leads to products of formula (IV).
[0032] EXAMPLE: Depolymerization of lignin obtained from the F315 commercial wood sawdust mixture (extracted by the AVIDEL process) using (RPOCOP) Ir (H) (acetone) 11-13 (C6F5) 4) and triethylsilane (Et3Sill) The depolymerization of the lignin resulting from the mixture of wood F315 (sawdust mixture marketed by the company SPPS extracted from species belonging to the family Pinaceae) is carried out following the general operating procedure depolymerization described above. In the case where the complex (RPOCOP) Ir (H) (acetone)] + B (C6F5) 4-) is used for the depolymerization of lignin, the procedure is similar to that where the catalyst employed is B (C6F5) 3. Et2SiH2 (5 mol.L-1) is used as a silane in chlorobenzene.
[0033] The mass of the lignin corresponds to 30% of the added silane mass. The reaction is carried out in the presence of 25% by weight of catalyst (mass calculated with respect to the mass of lignin added). The addition time of the silane and the catalyst is 30 min. The reaction time is of the order of 24 hours. Then, the solvent and the volatiles are evaporated, and the viscous liquid obtained is purified on a silica column (see general procedure).
[0034] The hydrolysis of the products from the column is carried out by stirring the products for 16 hours in a solution of 2 M HCl in THF. Finally, the various corresponding polyols are obtained by evaporation of the solvent and volatiles under vacuum. Hydrolysis of the mixture leads to products of formula (IV). EXAMPLE 10 Depolymerization of lignin obtained from the mixture of wood F315 (rich in unit G) (extracted with ethanol) with triethylsilane (Et3SiH) The lignin obtained from the mixture of wood F315 (sawdust mixture marketed by the company SPPS extracted from species belonging to the Pinaceae family) was extracted with ethanol and in the presence of hydrochloric acid in a catalytic amount, according to the method described by S. Bauer, H. Sorek, VD Mitchell, AB Ibeiez, DE Wernmer, .1. Agric. Food Chem. 2012, 60, pages 8203-8212.
[0035] The same procedure used for the depolymerization of lignin from the plane tree is used. This method leads to a total solubilization of the lignin as well as obtaining a mixture of products. Among the most volatile products, Ha and lib are identified by NMR and GC5 MS as shown in Table 1. The hydrolysis of the mixture leads to products of formula (TV). EXAMPLE 11: Depolymerization of the lignin obtained from the mixture of wood F315 (rich in unit G) (extracted by methanol) with triethylsilane (Et3Sill) The lignin of the wood mixture F315 (sawdust mixture marketed by the company SPPS extracts of species belonging to the Pinaceae family) was extracted by methanol, according to the method described by K. Barta, GR Warner, ES Beach, PT Anastas, Green Chem., 2014, 16, pages 191-196. The same procedure used for the depolymerization of lignin from Platane is used. This method leads to a total solubilization of the lignin and its depolymerization generating a product mixture. Among the most volatile products Ha and IIb are identified by NMR and by GCMS as indicated in Table 1. The hydrolysis of the mixture leads to products of formula (IV). EXAMPLE 12: Depolymerization of the lignin obtained from the mixture of wood F315 (rich in unit G) (extracted with acetone) with triethylsilane (Et3SiH) The lignin of the wood mixture F315 (sawdust mixture marketed by the company SPPS extracted from species belonging to the family Pinaceae) was extracted with acetone and in the presence of hydrochloric acid in catalytic amount, according to the method described by S. Bauer, H. Sorek, Mitchell VD, AB Ibeez, DE Wemrner, 25 Agric. Food Chem. 2012, 60, pages 8203-8212. The same procedure used for the depolymerization of lignin from Platane is used. This method leads to a total solubilization of lignin as well as obtaining a mixture of products of general formula II. Among the most volatile products, lb is identified by NMR and GC-MS as shown in Table 1. Hydrolysis of the mixture results in products of formula (IV).
[0036] EXAMPLE 13 (Comparative): Depolymerization with triethylsilane (Et3SiH) of commercial lignin (Aldrich: alkaline lignin sulphite) resulting from the sulphite then desulfurized process using sodium hydroxide The same procedure used for the depolymerization of lignin obtained from Eucalyptus (Eucalyptus camaldulensis) is used for the depolymerization of lignin from the sulphite process and having a sulfur content of 3.76% by mass relative to the total mass of lignin. No solubilization or depolymerization has been observed in the case of this lignin. In the case where the same sample of lignin is reprocessed by the AVIDEL process, the sulfur content reaches 3% by mass relative to the total mass of the lignin, but the depolymerization is still not carried out. This implies that the presence of sulfur in the reaction medium plays a crucial role in the deactivation of the reaction. The compounds of formulas (IV) obtained after the hydrolysis of the silylated compounds resulting from the depolymerization of lignin are of formula (IV) wherein R8, R9 and Rm represent, independently, one of the following: on the other, a hydrogen atom, a hydroxyl group; Y represents an alkyl group, an alkenyl group, an aleynyl group, a carbonyl group -CR4 = O with R4 representing a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, the said alkyl, alkenyl and alkynyl groups being optionally substituted. Table 1 summarizes the depolymerization results of the lignins of the examples indicated above.
[0037] Source of mass Mass Method lia mass mass III mass lignin extraction IId of lignin lignin used extracted F315 reflux of 2 15 - 1 - methanol Pin parasol AVIDEL = 8 16 - - - Thuya AVIDEL 7 8 - 2 giant Spruce AVIDEL 6 16 - 18 - common F315 reflux 3 13 - 15 - ethanol F315 reflux 2 - - 4 acetone Beech AVIDEL 14 13 22 - - common Poplar AVIDEL 17 19 21 from Italy Birch AVIDEL 13 10 26 - - during Oak green AVIDEL 12 6 37 - 13 Palm- AVIDEL 10 3 6 10 79 date palm Eucalyp- AVIDEL 9 8 30 17 35 tus Plum AVIDEL 18 20 3 26 green Platane AVIDEL 10 - 15.6 9 65 Cedar from AVIDEL 6 14 - 3 - Lebanon AVIDEL Fir Tree 20 2 - - - Nordmann AVIDEL Ebony 7 - - 6 Gabon In Table 1:% lignin extracted means the mass percentage of lignin extracted in relation to the wood mass initially used; mass% means the mass percentage of the species relative to the mass of initial lignin introduced evaluated by an external calibration of the GC-MS by the same molecules analyzed. The operating conditions applied to obtain the results of Table 1 are as follows: Lignin, Et3Sill (275 to 320% mass / mass lignin), B (C6F5) 3 (15 to 25% mass / mass lignin), CH2Cl2 (995% by weight) / lignin mass), 25 ° C, 16 hours.

权利要求:
Claims (12)
[0001]
REVENDICATIONS1. Process for the depolymerization of lignin into molecules containing from 1 to 2 aromatic rings, by selective cleavage of the sp3-oxygen carbon bond of alkylaryl ethers present in lignin, characterized in that the reaction is carried out in the presence of a catalyst a lignin with a sulfur content of less than 1.5% by weight, relative to the total mass of lignin, with a silane compound of formula (I) (1) in which - R ', R2 and R3 represent, independently of one another, a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a group silyl, a siloxy group, an aryl group, an amino group, said alkyl, alkenyl, alkynyl, alkoxy, silyl, siloxy, aryl and amino groups being optionally substituted, or R3 is as defined above and R1 and R2, taken together with the silicon atom to which they are attached form a hetero rocycle silyl optionally substituted.
[0002]
2. Method according to claim 1, characterized in that the depolymerization of the lignin by selective cleavage of the sp3-oxygen carbon bond of the alkylaryl ethers is aimed at the [3-0-4, aO-4, 3- 5, f3-1, [341 of the lignin.
[0003]
3. Method according to one of claims 1 or 2, characterized in that the sulfur content of the lignin is equal to or greater than zero and remains less than less than 1.5% by weight, relative to the total mass. lignin, as defined below: 0 <lignin sulfur content <1.5% by weight, based on the total mass of the lignin.
[0004]
4. Method according to any one of claims 1 to 3, characterized in that in the silane compound of formula (I), RI, R2 and R3 represent, independently of one another, a hydrogen atom; an alkyl group selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers; an alkoxy group whose alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers; an aryl group selected from benzyl and phenyl groups; a silyl group selected from polydimethylsiloxane (PDMS) and polymethylhydroxysiloxane (PMHS) and tetramethyldisiloxane (TMDS).
[0005]
5. Method according to any one of claims 1 to 4, characterized in that the catalyst is an organic catalyst selected from: carbocations selected from trityl cation ((C6H5) 3C +), tropilium (C7H7) +, cation benzyl (C6H5CH2 +), allyl cation (CH3-CH + -CH = CH2), methylium (CH3 ÷), cyclopropylium (C3H5 +), cyclopropyl carbocation selected from cyclopropyl dimethyl carbocation and dicyclopropyl carbocation, acylium (R1-C). = 0) + with RI selected from methyl, propyl and benzyl, benzenium cation (C6H5) +, norbomyl cation (C7Hii) +; oxoniums selected from (CH3) 30 + 13F4 and (CH3CF12) + 13F4-; a silylium ion (RI) 3Si + with R1 as defined in claim 1, selected from Et3Si + and Me3Si +; Disilyl cations having a bridging hydride selected from the formulas shown below wherein said carbocations and said disilyl cations are a halide selected from F-, Cl-, Br- - and; or * an anion selected from BEI-, ShF6-, B (C6F5) 4-, B (C6H5) 4-, CF3SO3-, PF6-.
[0006]
6. Process according to any one of claims 1 to 4, characterized in that the catalyst is an organometallic catalyst chosen from: - the iridium complexes of formula (III) R6 --- NRS R7 S R6 Formula (III Y- wherein - R6 represents an alkyl or aryl group; R7 represents a hydrogen atom or an alkyl group; and - X2 represents a -CH2- group or an oxygen atom; Y is a counterion selected from B (C6F5) 4 and B (C6H5) 4; S represents a solvent molecule, coordinated to the complex, chosen from dimethylsulfoxide (DMSO), acetonitrile (CH3CN) and acetone (CH3COCH3); and ruthenium complexes of formula (V) + R12Formula (V) wherein R12 represents a hydrogen atom or an alkyl group; R13 represents an aryl or an alkyl group, said aryl and alkyl groups being optionally substituted; Z is -CH2-, oxygen or sulfur; K represents a counterion selected from B (C6F5) 4 and [CHBHH5C161 '.
[0007]
7. Method according to any one of claims 1 to 4 and 6, characterized in that the organometallic catalyst is selected from 111 iridium complex RPOCOP) Ir (H) (acetone) j + B (C6F44- with POCOP ) representing 2,6-bis (di-tert-butylphosphinito) phenyl, and - the ruthenium complex of formula (V) in which - R12 represents a methyl group, R13 represents p-FC6H4, - Z represents a sulfur atom K represents B (C6F5) 4 '.
[0008]
8. Method according to any one of claims I to 4, characterized in that the catalyst is of Lewis acid type selected from: - boron compounds selected from BF3, BF3 (Et20), BC13, BBr3, triphenyl hydroborane, tricyclohexyl hydroborane, B (C6F5) 3, B-methoxy-9-borabicyclo [3.3.11nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane (B-benzyl) -9-BBN); - the borenium compound Me-TBD-BBN +, the borenium ferrocene derivatives corresponding to the formula borenium ferrocene in which R.1 is a phenyl group and R3 is 3,5-dimethylpyridyl, the aluminum compounds chosen from AlCl3, AlBr3 aluminum isopropoxide Al (O-i-Pr) 3, aluminum ethanoate (Al (C2H302)), Kxossing salt rAg (CH2C12)] {A1 {0C (CF3) 3] 4} Li {Al [OC (CF 3) 3] 4}, Et 2 AF; indium compounds selected from InC13, In (01T) 3; iron compounds selected from FeCl 3, Fe (OTf) 3; tin compounds selected from SnCl.sub.14, Sn (OTO.sub.2), phosphorus compounds such as PCl 3, PCl 5, POCl 3, trifluoromethanesulphonate or triflate (CF 3 SO 3) compounds of transition metals and lanthanides selected from scandium triflate, ytterbium triflate, yttrium triflate, cerium triflate, samarium triflate, niodinium triflate.
[0009]
9. Process according to any one of claims 1 to 4 and 8, characterized in that the catalyst is selected from BF3; InC13; triphenylcarbenium tetrakis (perfluorophenyl) borate [(Ph) 3C + B (C6F5) 4-, B (C6F5) 3] -
[0010]
10. Process according to any one of claims 1 to 9, characterized in that the reaction is carried out under a pressure of one or a mixture of inert gas (s) chosen (s) from nitrogen and argon, or gases generated by the process including methane and hydrogen, said pressure being between 0.2 and 50 bar, inclusive.
[0011]
11, Process according to any one of claims 1 to 10, characterized in that the reaction is carried out at a temperature between 0 and 150 ° C inclusive.
[0012]
12. Process according to any one of Claims 1 to 11, characterized in that the reaction is carried out in one or a mixture of at least two solvent (s) chosen from: - the silyl ethers chosen from 1 1,1,3,3,3-hexamethyldisiloxane ((Me3Si) 20), 1,1,1,3,3,3-hexaethyldisiloxane ((Et3Si) 20); hydrocarbons chosen from benzene, toluene, pentane and hexane; sulfoxides chosen from dimethyl sulphoxide (DMSO); the alkyl halides chosen from chloroform, methylene chloride, chlorobenzene and dichlorobenzene. Process according to any one of Claims 1 to 12, characterized in that the mass ratio between the silane compound of formula (I) and the lignin is between 0.5 and 6 inclusive. 14. Process according to any one of Claims 1 to 13, characterized in that the amount of catalyst is from 0.001 to 1 weight equivalent, inclusive limits, relative to the initial mass of lignin. 15. Use of a lignin depolymerization process according to any one of claims 1 to 15, in the manufacture of fuels, electronic components, plastic polymers, rubber, drugs, vitamins, cosmetics, perfumes, food products, synthetic yarns and fibers, synthetic leathers, glues, pesticides, fertilizers.

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公开号 | 公开日

FR3023555B1|2017-12-22|

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WO2016005836A1|2016-01-14|

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US10370315B2|2019-08-06|

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优先权:

申请号 | 申请日 | 专利标题

FR1456637A|FR3023555B1|2014-07-09|2014-07-09|PROCESS FOR DEPOLYMERIZING LIGNIN|FR1456637A| FR3023555B1|2014-07-09|2014-07-09|PROCESS FOR DEPOLYMERIZING LIGNIN|

PCT/IB2015/054567| WO2016005836A1|2014-07-09|2015-06-17|Method of depolymerizing lignin|

US15/322,866| US10370315B2|2014-07-09|2015-06-17|Method of depolymerizing lignin|

EP15736636.0A| EP3166916B1|2014-07-09|2015-06-17|Method of depolymerizing lignin|

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