# US 2008/0188636 A1 · Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2008/0188636 A1 - Document ID: US20080188636A1 - Status: Published application - Kind: A1 - Application number: 12/026,998 - Filed: 2008-02-06 - Published: 2008-08-07 - Earliest claimed: 2007-02-06 - Assignees: North Carolina State University - Inventors: Dimitris Argyropoulos; Haibo Xie - Web page: https://patentgrep.com/patent/US20080188636A1 ## CPC - C08L 71/02: Polyalkylene oxides - C08H 8/00: Macromolecular compounds derived from lignocellulosic materials {(pretreatment thereof B27N)} - C08L 29/04: Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids - C08L 97/005: {Lignin} - C08L 97/02: Lignocellulosic material, e.g. wood, straw or bagasse {(manufacture of articles made from lignocellulosic material by dry processes B27N)} - C08L 33/20: Homopolymers or copolymers of acrylonitrile (C08L55/02 takes precedence) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C08H: DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS (polysaccharides C08B; natural rubber C08C; natural resins or their derivatives C09F; bituminous materials C10) ## Abstract The present invention provides wood derivatives and composite materials prepared by first solvating a lignocellulosic material using an ionic liquid. The solvated lignocellulosic material can be derivatized to incorporate functional groups, particularly groups that facilitate later combination with polymer materials, including non-polymer polymers. The polymeric materials can be combined with the derivatized lignocellulosic material in solution, or the derivatized lignocellulosic material can be isolated and later combined with the polymeric material in a melt. The invention encompasses a variety of wood derivatives, composites, and nanocomposites useful for preparing multiple types of products, including membranes, fibers, and formed parts. ## Claims ### Claim 1 A composite material comprising an ionic liquid solvated lignocellulosic material in combination with a further polymeric component. ### Claim 2 (depends on 1) The composite material according to claim 1, wherein the further polymeric component comprises a natural polymer. ### Claim 3 (depends on 1) The composite material according to claim 1, wherein the further polymeric component comprises a synthetic polymer. ### Claim 4 (depends on 1) The composite material according to claim 1, wherein the further polymeric component comprises a non-polar polymer. ### Claim 5 (depends on 1) The composite material according to claim 1, wherein the further polymeric component is selected from the group consisting of polysaccharides, polyesters, polyamides, aromatic polyamides, polyimides, polyurethanes, polysiloxanes, aromatic polymers, phenol polymers, polysulfides, polyacetals, polyolefins, halogenated polyolefins, polyethylene oxides, polyacrylates, polymethacrylates, polycarbonates, polydienes, and combinations thereof. ### Claim 6 (depends on 1) The composite material according to claim 1, wherein the solvated lignocellulosic material is a derivatized material. ### Claim 7 (depends on 6) The composite material according to claim 6, wherein the solvated lignocellulosic material is chemically derivatized through a reaction with one or more naturally occurring hydroxyl moiety present in the lignocellulosic material to add a different, derivatizing chemical moiety. ### Claim 8 (depends on 7) The composite material according to claim 7, wherein the derivatizing moiety comprises a carboxyl group that reacts with the hydroxyl moiety on the lignocellulosic material to form an ester linkage. ### Claim 9 (depends on 7) The composite material according to claim 7, wherein the derivatizing moiety comprises a halogen leaving group that reacts with the hydroxyl moiety on the lignocellulosic material to form an ether linkage. ### Claim 10 (depends on 7) The composite material according to claim 7, wherein the derivatizing moiety is selected from the group consisting of carboxylic acids, carboxylic esters, acyl halides, acyl pseudohalides, acid anhydrides, aldehydes, ketones, carboxamides, aliphatic halides, and combinations thereof. ### Claim 11 (depends on 1) The composite material according to claim 1, wherein the composite material is in the form of a liquid melt. ### Claim 12 (depends on 1) The composite material according to claim 1, wherein the composite material is in the form of a fiber or membrane. ### Claim 13 (depends on 1) The composite material according to claim 1, wherein the ionic liquid solvated lignocellulosic material comprises a wood. ### Claim 14 A derivatized lignocellulosic material, comprising a lignocellulosic material that has been chemically derivatized such that one or more naturally occurring hydroxyl moiety present in the lignocellulosic material has been replaced with a different, derivatizing chemical moiety. ### Claim 15 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the lignocellulosic material comprises an ionic liquid solvated lignocellulosic material. ### Claim 16 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the lignocellulosic material comprises a wood. ### Claim 17 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the derivatizing moiety comprises a carboxyl group that reacts with the hydroxyl moiety on the lignocellulosic material such that the derivatizing moiety is linked to the lignocellulosic material via an ester linkage. ### Claim 18 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the derivatizing moiety comprises a halogen leaving group that reacts with the hydroxyl moiety on the lignocellulosic material such that the derivatizing moiety is linked to the lignocellulosic material via an ether linkage. ### Claim 19 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the derivatizing moiety is selected from the group consisting of carboxylic acids, carboxylic esters, acyl halides, acyl pseudohalides, acid anhydrides, aldehydes, ketones, carboxamides, aliphatic halides, and combinations thereof. ### Claim 20 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the derivatized lignocellulosic material is solubilized in an ionic liquid. ### Claim 21 (depends on 14) The derivatized lignocellulosic material according to claim 14, wherein the derivatized lignocellulosic material is a solid. ### Claim 22 (depends on 21) The derivatized lignocellulosic material according to claim 21, wherein the derivatized lignocellulosic material is a powder. ### Claim 23 A method of preparing a composite material comprising dissolving a lignocellulosic material in an ionic liquid to form a solution and combining the solvated lignocellulosic material with a further polymeric component. ### Claim 24 (depends on 23) The method according to claim 23, wherein the further polymeric component comprises a natural polymer. ### Claim 25 (depends on 23) The method according to claim 23, wherein the further polymeric component comprises a synthetic polymer. ### Claim 26 (depends on 25) The method according to claim 25, wherein the further polymeric component comprises a non-polar polymer. ### Claim 27 (depends on 25) The method according to claim 25, wherein the further polymeric component is selected from the group consisting of polysaccharides, polyesters, polyamides, aromatic polyamides, polyimides, polyurethanes, polysiloxanes, aromatic polymers, phenol polymers, polysulfides, polyacetals, polyolefins, halogenated polyolefins, polyethylene oxides, polyacrylates, polymethacrylates, polycarbonates, polydienes, and combinations thereof. ### Claim 28 (depends on 23) The method according to claim 23, further comprising, prior to said combining step, derivatizing the solvated lignocellulosic material. ### Claim 29 (depends on 28) The method according to claim 28, wherein said derivatizing step comprises combining the solvated lignocellulosic material with a derivatizing chemical moiety to replace one or more naturally occurring hydroxyl moiety present in the lignocellulosic material with the different, derivatizing moiety. ### Claim 30 (depends on 29) The method according to claim 29, wherein the derivatizing moiety comprises a carboxyl group that reacts with the hydroxyl moiety on the lignocellulosic material to form an ester linkage. ### Claim 31 (depends on 29) The method according to claim 29, wherein the derivatizing moiety comprises a halogen leaving group that reacts with the hydroxyl moiety on the lignocellulosic material to form an ether linkage. ### Claim 32 (depends on 29) The method according to claim 29, wherein the derivatizing moiety is selected from the group consisting of carboxylic acids, carboxylic esters, acyl halides, acyl pseudohalides, acid anhydrides, aldehydes, ketones, carboxamides, aliphatic halides, and combinations thereof. ### Claim 33 (depends on 23) The method according to claim 23, wherein said combining step comprises melt processing or solution blending the solvated lignocellulosic material and the further polymeric component. ### Claim 34 (depends on 23) The method according to claim 23, wherein said combining step comprises adding the further polymeric component to the solution. ### Claim 35 (depends on 23) The method according to claim 23, further comprising, prior to said combining step, regenerating the solvated lignocellulosic material to form a solid, regenerated lignocellulosic material. ### Claim 36 (depends on 35) The method according to claim 35, wherein said combining step comprises mixing the regenerated lignocellulosic material with the further polymeric component to form a melt. ### Claim 37 (depends on 36) The method according to claim 36, further comprising extruding the melt to form composite fibers. ### Claim 38 (depends on 36) The method according to claim 36, further comprising molding to the melt to a desired form. ### Claim 39 (depends on 23) The method according to claim 23, wherein the ionic liquid comprises a material formed of a cation and an anion, wherein the cation is selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, delenozoles, oxaphospholes, pyrroles, boroles, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotetrazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines, guanidiniums, quinxalines, choline-based analogues, derivatives thereof, and combinations thereof, and wherein the anion is selected from the group consisting of halogens, phosphates, alkylphosphates, alkenylphosphates, BF4−, PF6−, AsF6−, NO3−, N(CN)2−, N(SO3CF3)2−, amino acids, substituted or unsubstituted carboranes, perchlorates, pseudohalogens, metal chloride-based Lewis acids, C1-6 carboxylates, and combinations thereof. ### Claim 40 (depends on 39) The method according to claim 39, wherein the cation is selected from the group consisting of imidazoles and pyridines, and the anion is selected from the group consisting of halogens, phosphates, alkylphosphates, alkenylphosphates, and bis(trifluoromethylsulfonyl)imide. ### Claim 41 (depends on 23) The method according to claim 23, wherein the lignocellulosic material is selected from the group consisting of tobacco, corn, corn stovers, corn residues, cornhusks, sugarcane bagasse, castor oil plant, rapeseed plant, soybean plant, cereal straw, grain processing by-products, bamboo, bamboo pulp, bamboo sawdust, energy grasses, rice straw, paper sludge, waste papers, recycled paper, recycled pulp, and combinations thereof. ### Claim 42 (depends on 41) The method according to claim 41, wherein the lignocellulosic material is a wood. ### Claim 43 (depends on 23) The method according to claim 23, wherein the lignocellulosic material, prior to dissolving in the ionic liquid, is in a form selected from the group consisting of ball-milled wood powder, sawdust, thermomechanical pulp fibers, wood chips, and combinations thereof. ### Claim 44 A method of preparing a derivatized lignocellulosic material comprising dissolving a lignocellulosic material in an ionic liquid to form a solution and combining the solvated lignocellulosic material with a derivatizing chemical moiety to replace one or more naturally occurring hydroxyl moiety present in the lignocellulosic material with the different, derivatizing moiety. ### Claim 45 (depends on 44) The method according to claim 44, wherein the derivatizing moiety comprises a carboxyl group that reacts with the hydroxyl moiety on the lignocellulosic material to form an ester linkage. ### Claim 46 (depends on 44) The method according to claim 44, wherein the derivatizing moiety comprises a halogen leaving group that reacts with the hydroxyl moiety on the lignocellulosic material to form an ether linkage. ### Claim 47 (depends on 44) The method according to claim 44, wherein the derivatizing moiety is selected from the group consisting of carboxylic acids, carboxylic esters, acyl halides, acyl pseudohalides, acid anhydrides, aldehydes, ketones, carboxamides, aliphatic halides, and combinations thereof. ### Claim 48 (depends on 44) The method according to claim 44, further comprising regenerating the derivatized lignocellulosic material to form a solid, regenerated derivatized lignocellulosic material. ### Claim 49 (depends on 44) The method according to claim 44, wherein the ionic liquid comprises a material formed of a cation and an anion, wherein the cation is selected from the group consisting of imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, delenozoles, oxaphospholes, pyrroles, boroles, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles, isotetrazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, annolines, phthalazines, quinazolines, guanidiniums, quinxalines, choline-based analogues, derivatives thereof, and combinations thereof, and wherein the anion is selected from the group consisting of halogens, phosphates, alkylphosphates, alkenylphosphates, BF4−, PF6−, AsF6−, NO3−, N(CN)2−, N(SO3CF3)2−, amino acids, substituted or unsubstituted carboranes, perchlorates, pseudohalogens, metal chloride-based Lewis acids, C1-6 carboxylates, and combinations thereof. ### Claim 50 (depends on 49) The method according to claim 49, wherein the cation is selected from the group consisting of imidazoles and pyridines, and the anion is selected from the group consisting of halogens, phosphates, alkylphosphates, alkenylphosphates, and bis(trifluoromethylsulfonyl)imide. ### Claim 51 (depends on 44) The method according to claim 44, wherein the lignocellulosic material is selected from the group consisting of tobacco, corn, corn stovers, corn residues, cornhusks, sugarcane bagasse, castor oil plant, rapeseed plant, soybean plant, cereal straw, grain processing by-products, bamboo, bamboo pulp, bamboo sawdust, energy grasses, wood, and combinations thereof. ### Claim 52 (depends on 51) The method according to claim 51, wherein the lignocellulosic material is a wood. ### Claim 53 (depends on 44) The method according to claim 44, wherein the lignocellulosic material, prior to dissolving in the ionic liquid, is in a form selected from the group consisting of ball-milled wood powder, sawdust, thermomechanical pulp fibers, wood chips, and combinations thereof.