WO1981003332A1 - Production de resines de lignine-cellulose et d'hydrates de carbone - Google Patents

Production de resines de lignine-cellulose et d'hydrates de carbone Download PDF

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Publication number
WO1981003332A1
WO1981003332A1 PCT/US1980/001092 US8001092W WO8103332A1 WO 1981003332 A1 WO1981003332 A1 WO 1981003332A1 US 8001092 W US8001092 W US 8001092W WO 8103332 A1 WO8103332 A1 WO 8103332A1
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Prior art keywords
weight
parts
cellulose
lignin
product
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PCT/US1980/001092
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English (en)
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David H Blount
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David H Blount
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Priority to AU63940/80A priority Critical patent/AU6394080A/en
Publication of WO1981003332A1 publication Critical patent/WO1981003332A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/0293—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with natural products, oils, bitumens, residues
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/08—Alkali cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass

Definitions

  • Cellulose-containing plants are broken down by mixing with an alkali metal hydroxide then heated to 150o C to 220o C while agitating for 5 to 60 minutes thereby producing a broken down alkali metal cellulose-containing plant, polymer then mixed with an acid compound until the pH is 5 to 7 thereby producing a lignin-cellulose resinous product and a mixture of carbohydrates.
  • This invention relates to a novel and economical process to break down particles of cellulose-containing plants into lignin-cellulose resinous products, CO 2 and carbohydrates.
  • the carbohydrates are then broken down into ethanol by fermentation.
  • U.S. Patent Application No. 013,139 filed February 21, 1979, by David H. Blount, M.D., it illustrated the process to break down cellulose containing plants into water soluble polymers, but did not include the discovery of carbohydrates being produced in the process.
  • the cellulose-containing plant such as wood
  • the cellulose-containing plant is broken down into water soluble alkali metal lignin-cellulose polymer, carbohydrates and sodium carbonate.
  • the lignin-cellulose bond is not broken in most of the cases, but the molecules of cellulose are broken into CO 2 and carbohydrates.
  • the carbohydrates appear to be a mixture with glucose being the predominent carbohydrate.
  • the alkali metal lignin-cellulose may be separated from the carbohydrate by using an organic solvent such as ketones, alcohols and many other solvents.
  • the carbohydrates produced by this process may be utilized to produce ethanol by fermentation as a food for animals and humans, and may be further reacted with organic epoxides, mono and polysubstituted organic compounds to produce new and useful products.
  • the lignin-cellulose resinous product may be used as an adhesive such as in producing plywood, in laminates, as filler, etc. and may be further reacted with aldehydes, aminoplasts, phenoplasts, epoxides, ketones, furfuryl alcohol, amines, isocyanates, polyamines, polyisocyanates, mono and polysubstituted organic compound such as polyhalides, monohalides, organic anhydrides, epihalohydrins, halohydrins and other organic compounds to produce useful resins which may be utilized as adhesives, as laminates, as coating agent, as molding agents, as foams.
  • the lignin-cellulose resinous products are soluble in common organic solvents such as ketones, alcohols, glycols, organic esters, etc.
  • Lignin-cellulose resinous products CO 2 and carbohydrates are produced by reacting the following components: component (a) : A cellulose-containing plant. component (b): An alkali metal hydroxide. component (c): A salt producing compound. component (a)
  • cellulose-containing plant or the products of cellulose-containing plants which contain cellulose may be used in this invention.
  • the plant material is preferred to be in the form of small particles such as sawdust. In nature, cellulose is widely distributed. It is found in all plants and they may be used in this process, preferably in a dry, small-particle form.
  • Suitable cellulose-containing plants include, but are not limited to, trees, e.g., spruce, pine, hemlock, fir, oak, ash, larch, birch, aspen, poplar, cedar, beech, maple, walnut, cypress, redwood, cherry, elm, chestnut, hickory, locust, sycamore, tulip, tupelo, butternut, apple, alder, magnolia, dogwood, catalpa, boxwood, crabwood, mahogany, greenheart, lancewood, letterwood, mora, prima vera, purpleheart, rosewood, teak, satinwood, mangrove, wattle, orange, lemon, logwood, fustic, osage orange, sappanwood, Brazilwood, barwood, camwood, sandalwood, rubber, gutta, mesquite, and shrubs, e.g., oleander, cypress, junipers, acanth
  • Wood fibers and cotton fibers are the pre ferred cellulose-containing materials.
  • the waste products of agricultural plants which contain cellulose may be air-dried, then ground into small particles and used in this invention.
  • Commercial waste products containing cellulose e.g., paper, cotton cloth, bagasse wallboard, wood products, etc., may be used in this invention.
  • Wood with the lignin removed (wood pulp) may be. used in this invention.
  • Cellulose-containing plants which have been partially decomposed such as humus, peat and certain soft brown coal, may be used in this invention.
  • alkali metal compounds are preferred such as alkali metal oxides, alkali metal hydroxide, alkali metal silicates and mixtures thereof. Mixtures of sodium hydroxide and calcium hydroxide may be used. Suitable alkali metal hydroxides include sodium hydroxide, potassium hydroxide and mixtures thereof. Sodium hydroxide is the preferred alkali compound. component (c)
  • Suitable salt forming compounds include mineral acids, organic acid, organic acid halides, hydrogen containing acid salts, e.g., sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate and mixtures thereof. Mineral acids are preferred especially sulfuric acid and hydrochloric acid.
  • Any suitable yeast consisting of a mass of minute fungi which germinate and multiply in the presence of carbohydrates and forms ethanol and carbon dioxide during a process of fermentation induced by an enzyme may be used in this invention in the production of ethanol from the carbohydrates produced by the process of this invention.
  • Any suitable method may be used to ferment the carbohydrates produced by the process of this invention to produce ethanol.
  • Any suitable yeast which ferments a carbohydrate to produce ethanol may be added to an aqueous solution containing 10% to 40% by weight of carbohydrates produced by the process of this invention then 5 grams of yeast per 1 to 5 gallons of the aqueous solution of carbohydrates is added.
  • the yeast may be sprinkled on top of the solution at a temperature of 70o to 80 F for 12 hours then stirred in after 12 hours. Stir extremely well and make a lot of bubbles in it. Oxygen from the air helps the yeast grow.
  • the mixture is fermented for up to 2 weeks or until the carbohydrates are used up.
  • the ethanol is then recovered by distillation.
  • aldehyde any suitable aldehyde may be used in this invention, such as formaldehyde, acetaldehyde, butyl aldehyde, chloral, acrolein, furfural, benzaldehyde, crotonaldehyde, propionaldehyde, pentanals, hexanals, heptanals, octanals and their simple substitution products, semi-acetate and full acetals, paraformaldehyde and mixtures thereof.
  • Compounds containing active aldehyde groups such as hexamethylene tetramine may also be used.
  • Any suitable amino compound may be used in this invention such as urea, thiourea, alkyl-substituted thiourea, alkyl-substituted ureas, melamine, aniline, quanidine, saccharin, dicyandiamide, benzene sulfonamides, toluene sulfonamide, aliphatic and aromatic polyamines and mixtures thereof.
  • Urea is the preferred amino compound
  • formaldehyde is the preferred aldehyde when used with an amino compound.
  • Any suitable phenol compound may be used in this invention such as phenol, p-cresol, o-cresol, m-cresol, cresylic acid, xylenols, resorcinol, cashew nut shell liquids, anacordol, p-tert-but ⁇ l phenol, Bisphenol A, creosote oil, 2,6-dimethylphenol and mixtures thereof.
  • Phenol is the preferred phenol compound and formaldehyde is the preferred aldehyde when used with a phenol compound.
  • thermosetting phenol-formaldehyde and urea-formaldehyde resins may be used in this invention.
  • Any suitable mixture of the amino compounds and phenol compounds with an aldehyde may be used in this invention.
  • Any suitable acid compound, inorganic or organic, may be used for salt formation, and as an acid catalyst, including those which also have a chainbuilding function such as sulphurous acid, sulphuric acid, hypophosphorous acid, phosphinic acids, phosphonous acids and phosphonic acid, glycolic acid, lactic acid, succinic acid, tartaric acid, oxalic acid, phthalic acid, trimellitic acid and the like. Further examples of acids may be found in German Patent No. 1,178,586 and in U. S. Patent No. 3,480,592. Acids such as hydrochloric, fluoroboric acid, amidosulphonic acid, phosphoric acid and its derivatives, acetic acid, propionic acid, etc., may be used.
  • Inorganic hydrogen-containing salts may be used such as sodium hydrogen sulphate, potassium hydrogen sulphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and mixtures thereof.
  • the acid compounds may be used to react with the alkali metal atoms in the broken down alkali metal, cellulose-containing plant polymer to produce a salt and also release CO 2 .
  • the acid compounds may also be used as a catalyst in the reactions to produce poly(aminoplast-lignin-cellulose) resinous products, and foam poly(phenoplast-lignin-cellulose) resinous products and foam and poly(aminoplast-lignin-cellulose-phenoplast) resinous and foamed products.
  • Any suitable oxidated silicon compound may be used in this invention such as silica, e.g., hydrated silica, silicoformic acid, silica sol, etc., alkali metal silicates, alkaline earth metal silicates, natural Silicates with free silicic acid groups and mixtures thereof.
  • the hydrated silica includes various silicon acids such as silicic acid gel, ortho-silicic acid, metasilicic acid, monosilandiol, polysilicoformic acid, etc. Hydrated silica is the preferred oxidated silicon compound.
  • Any suitable organic polyisocyanate may be used according to the invention, including aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates.
  • Suitable polyisocyanates for example, arylene polyisocyanates such as tolylene, metaphenylene; 4-chlorophenylene-1,3-; methylene-bis-(phenylene-4-) ; biphenylene-4,4'-; 3,3-dimethyoxy-biphenylene-4,4' - ; 3,3' -diphenylbiphenylene-4,4' - ; naphthalene-1,5- and tetrahydronaphthalene-1,5-diisocyanates and triphenylmethane triisocyanate; alkylene polyisocyanates such as ethylene, ethylidene; propylene-1,2-; butylene-1,4-; butylene-1,3-; hexylene-1,
  • methylene-bis-(cyclohexyl-4,4'-) diisocyanates It is generally preferred to use commercially readily available polyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers, (“TDI”), polyphenyl-polymethylene-isocyanates obtained by aniline-formaldehyde condensation followed by phosgenation (“crude MDI”), and polyisocyanates which contain carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups, ("modified polyisocyanates").
  • polyisocyanates e.g., tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers, (“TDI”)
  • TDI polyphenyl-polymethylene-isocyanates obtained by aniline-formaldehyde
  • Inorganic polyisocyanates are also suitable according to the invention. Suitable polyisocyanates which may be used according to the invention are described, e.g., by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136.
  • Solutions of distillation residues accumulating during the production of tolylene diisocyanate, diphenyl methane diisocyanate or hexamethylene diisocyanate, in monomeric polyisocyanates or in organic solvents and mixtures thereof may be used in this process.
  • Phosgenation products of condensates of aniline or anilines alkylsubstituted on the nucleus, with aldehydes or ketones, may be used in this invention.
  • Organic polyhydroxyl compounds may be used in this invention with polyisocyanates or may be first reacted with a polyisocyanate to produce isocyanate-terminated polyurethane prepolymers and then also used in this invention.
  • Reaction products of from 50 to 99 mols of aromatic diisocyanates with from 1 to 50 mols of conventional organic compounds with a molecular weight of, generally, from about 400 to about 10,000, which contain at least two hydrogen atoms capable of reacting with isocyanates, may also be used.
  • organic polyhydroxyl compounds in particular, compounds which contain from 2 to 8 hydroxyl groups, especially those with a molecular weight of from about 800 to about 10,000 and preferably from about 1,000 to about 6,000, e.g., polyesters, polyethers, polythioethers, polyacetals, polycarbonates or polyester amides containing at least 2, generally from 2 to 8, but preferably from 2 to 4, hydroxyl groups, of the kind known for producing homogenous and cellular polyurethanes.
  • the hydroxyl group containing polyesters may be, for example, reaction products of polyhydric alcohols, preferably dihydric alcohols, with the optional addition of trihydric alcohols, and polybasic, pre ferably dibasic, carboxylic acids.
  • polyhydric alcohols preferably dihydric alcohols
  • polybasic, pre ferably dibasic, carboxylic acids instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures may be used for preparing the polyesters.
  • the polycarboxylic acid may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted, e.g., with halogen atoms and may be unsaturated.
  • Examples include: succinic acid, adipic acid, sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalic acid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride, trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, fumaric acid, maleic acid, maleic acid anhydride, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethylterephthalate and bis-glycol terephthalate.
  • Any suitable polyhydric alcohol may be used such as, for example, ethylene glycol; propylene-1,2- and -1,3-glycol; butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol; neopenthl glycol; cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane); 2-methyl propane-1,3-diol; glycerol; trimethylol propane; hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane; pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycols; dipropylene glycol; polypropylene glycols; dibutylene glycol
  • the polyethers with at least 2, generally from 2 to 8 and preferably 2 or 3, hydroxyl groups used according to the invention are known and may be prepared, e.g., by the polymerization of epoxides, e.g., ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, each with itself, e.g., in the presence of BF 3 , or by addition of these epoxides, optionally as mixtures or successively, to starting components which contain reactive hydrogen atoms such as alcohols or amines, e.g., water, ethylene glycol; propylene-1,3 or 1-2-glycol; trimethylolpropane; 4,4-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine or ethylenediamine.
  • epoxides e.g., ethylene oxide, propylene oxide, butylene oxide, te
  • Sucrose polyethers such as those described, e.g., in German Auslegeschriften Nos. 1,176,358 and 1,064,938, may also be used according to the invention. It is frequently preferred to use polyethers which contain predominantly primary OH groups, (up to 90% by weight, based on the total OH groups contained in the polyether) .
  • Polyethers modified with vinyl polymers such as those which may be obtained by polymerizing styrene or acrylonitrile in the presence of polyethers, (U. S. Patent Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110,695; and German Patent No. 1,152,536) and polybutadienes which contain OH groups are also suitable.
  • polythioethers are meant, in particular, the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols.
  • the products obtained are polythio-mixed ethers or polythioether ester amides, depending on the cocomponent.
  • the polyacetals used may be, for example, the compounds which may be obtained from glycols, e.g., diethylene glycol, triethylene glycol, 4,4'-dihydroxydiphenylmethylmethane, hexanediol, and formaldehyde.
  • Polyacetals suitable for the invention may also be prepared by the polymerization of cyclic acetals.
  • the polycarbonates with hydroxyl groups used may be of the kind, e.g., which may be prepared by reacting diols, e.g., propane-1,3-diol; butane-1,4-diol; and/or hexane-1,6-diol or diethylene glycol; triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g., diphenylcarbonates or phosgene.
  • diols e.g., propane-1,3-diol
  • butane-1,4-diol and/or hexane-1,6-diol or diethylene glycol
  • diarylcarbonates e.g., diphenylcarbonates or phosgene.
  • polyester amides and polyamides include, e.g., the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof.
  • Polyhydroxyl compounds which already contain urethane or urea groups, modified or unmodified natural polyols, e.g., castor oil, carbohydrates and starches, may also be used. Additional products of alkylene oxides with phenolformaldehyde resins or with resin-formaldehyde resins are also suitable for the purpose of the invention.
  • the polyisocyanates or the prepolymer which contains NCO groups have a viscosity above 2000 cP at 25o C, it may be advantageous to reduce the viscosity thereof by mixing it with a low-viscosity organic polyisocyanate and/or an inert blowing agent or solvent.
  • Inorganic polyisocyanates and isocyanate-terminated polyurethane silicate prepolymers may also be used in this invention.
  • catalysts such as tertiary amines, e.g., triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, tetramethylthylenediamine, pentamethyldiethylenetriamine, triethanolamine, triisoprophanolamine, organo-metallic compound, e.g., tin acetate, tin octoate, tin ethyl hexoate, dibutyl tin diacetate, dibutyl tin dilaurate and mixtures thereof.
  • tertiary amines e.g., triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, tetramethylthylenediamine, pentamethyldiethylenetriamine, triethanolamine, triisoprophanolamine, organo-metallic compound, e.g.
  • catalysts which may be used according to the invention and details of their action are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff, 1966, e.g., on pages 96 and 102.
  • Sila-amines are suitable catalysts, e.g., 2,2-4-trimethyl-2-silamorpholine or 1,3-diethyl aminomethyl tetramethyl disiloxane.
  • Suitable catalysts are also tetraalkyl ammonium hydroxides, alkali phenolates, alkali metal hydroxides, alkali phenolates, alkali-alcoholates and hexahydrotriazines.
  • Suitable flame-resistant compounds may be used which contain halogen or phosphorus, e.g., tributylphosphate; tris(2,3-dichloropropyl)-phosphate; polyoxypropylenechloromethylphosphonate; cresyldiphenylphosphate; tricresylphosphate; tris-(beta-chloroethyl)-phosphate; tris-(2,3-dichloropropyl)-phosphate; triphenyl-phosphate; ammonium phosphate; perchlorinated diphenyl; perchlorinated terephenyl; hexabromocyclodecane; tribromophenol; dibromopropyldiene; hexabromobenzene; octabromodiphenylether; pentabromotoluol; poly-tribromostyrol; tris-(bromocresyl)-phosphate; tetrabromobi
  • the organic halogen-containing components are, however, preferred in the polyurethane-cellulose and polyurethane-cellulose-silicate cellular solid products.
  • phosphoric acid may be used to react with the alkali metal atoms, thereby producing an alkali metal hydrogen phosphate which may be .used as the flame-resistant compound.
  • Alkali metal silicates may be used as flame-resistant compounds.
  • Any suitable water-binding agent may be used in this invention such as hydraulic cement, burnt lime, gypsum and synthetic anhydrites.
  • Hydraulic cements such as Portland cement, quick-setting cement, mortar cement, blast-furnace Portland cement, sulphate-resistant cement, brick cement, mild-burnt cement, natural cement, lime cement, gypsum cement, calcium sulfate cement, pozzolan cement, etc., contain oxidated silicon compounds and may be used in this invention.
  • cement there are many different kinds of cement which may be used; in general, any mixture of fine ground lime, alumina and silica that will set to a hard product by admixture of water which combines chemically with the other ingredients to form a hydrate may be used.
  • Detailed descriptions of the many kinds of cement which react with sand and rocks to produce concrete may be found in "Encyclopedia of Chemically Technology", Volume 4, Second Edition, Published by Kirk-Othmer, pages 684 to 710, as well as in other well known references in this field.
  • the preferred process to produce lignin-cellulose, carbohydrates and carbon dioxide is to mix about 2 parts by weight of air-dried fine particles of a cellulose-containing plant with 1 to 3 parts by weight of an alkali metal hydroxide which is at a temperature of 150° C to 220o c while agitating for 5 to 60 minutes, thereby producing a water soluble broken down alkali metal cellulose-containing plant polymer, then a salt forming compound is mixed with the broken down alkali metal cellulose-containing plant polymer in an amount wherein the acid radical are about equal to or greater than the alkali metal radicals thereby producing a mixture of lignin-cellulose resinous product, CO 2 , carbohydrates and salt; water is then added to the mixture until a solution is produced that contains 20% to 70% solids. The pH is then adjusted to a pH of 5 to 6.5 and the lignin-cellulose resinous product floats to the top and is separated from the aqueous solution of carbohydrates by filtration or decantation.
  • the aqueous solution of carbohydrates is then fermented by adjusting the pH to 6.5 to 7 then adding 5 grams of a fermenting yeast to 1 to 5 gallons of the aqueous solution of carbohydrates containing 10% to 40% solids at 75 to 80o F for up to
  • the solution may be distilled several times.
  • the carbohydrates are recovered by evaporating the water under reduced pressure and allowed to crystallize.
  • the uncrystallized portion is removed by centrifuging.
  • the centrifugate is reconcentrated, and the operation is repeated until no more crystals can be obtained.
  • the crystallized carbohydrates may be diluted with water then fermented to produce ethanol.
  • the broken down alkali metal cellulose containing plants is added to water to produce an aqueous solution in an amount to produce a solution containing 10% to 50% solids, then a salt forming compound, e.g., mineral acids, organic acids, hydrogen containing salts, etc., is added until the pH is 3 to 6.5 thereby producing a lignin-cellulose resinous product which floats on top of the water, CO 2 and an aqueous solution of carbohydrates and salt.
  • a salt forming compound e.g., mineral acids, organic acids, hydrogen containing salts, etc.
  • reaction may take place in an aqueous solution at a pH of .8 to 10 or a pH of
  • a phenol compound 0.5 to 5 parts by weight of a phenol compound, 0.5 to 5 parts by weight of an aldehyde and 2 parts by weight of the lignin-cellulose resinous product produced by the process of this invention are mixed and the resultant mixture is reacted, the reaction may take place in an aqueous solution with a pH of 8 to 12 or a pH of 3 to 7, thereby producing a poly(aldehyde-phenol-lignin-cellulose) resinous product.
  • thermosetting resin of the class consisting of the thermosetting ureaformaldehyde resins and melamine-formaldehyde resins and 2 parts by weight of the lignin-cellulose resinous product produced in this invention are mixed then reacted under heat (220 to 300o F) and pressure (150 to 250 psi) for 1 to 10 minutes thereby producing an aminoplast-lignin silicate resinous product.
  • thermosetting phenol-aldehyde resin selected from the group consisting of phenol-formaldehyde resin, phenol-resorcinol-formaldehyde resin, resorcinol-formaldehyde resin and mixtures thereof and 2 parts by weight of lignin-cellulose, resinous product as produced in this invention are mixed and reacted by heat (220 F to 300o F) and pressure (150 to 250 psi) for 1 to 10 minutes thereby producing a phenoplast-lignin-cellulose resinous product.
  • Paraformaldehyde may also be added with the thermosetting phenol-aldehyde resin in an amount of 0.5 to 3 parts by weight.
  • lignin-cellulose resinous product produced by the process of this invention, are mixed; the resultant mixture is reacted, the reaction may take place in an aqueous solution with a pH of 8 to 12 or a pH of 3 to 7, thereby producing a phenoplast-lignin-cellulose-aminoplast resinous product.
  • 2 parts by weight of the lignin-cellulose resinous product, produced by the process of this invention, and 1 to 4 parts by weight of an organic polyisocyanate are mixed, then agitated for 10 to 60 minutes at a temperature between 20o C to 70° C, thereby producing a poly(polyisocyanate lignin-cellulose) prepolymer; then 10% to 100% by weight of a curing agent, based on the weight of the prepolymer, is added to the poly(polyisocyanate lignin-cellulose) prepolymer while agitating at 20o C to 80o C for 5 to 20 minutes, thereby producing a cellular solid or solid poly(polyisocyanate lignin-cellulose) product.
  • 1 to 3 parts by weight of the lignin-cellulose resinous product as produced by the process of this invention,1 to 3 parts by weight of a polyol, 1 to 10 parts by weight of a water-binding agent, 1 to 10 parts by weight of a filler, 1 to 3 parts by weight of an organic polyisocyanate, up to 10% by weight of a filler, 1 to 3 parts by weight of an organic polyisocyanate, up to 10% by weight of an amine catalyst and up to 50% by weight of an inert volatile blowing agent, percentage based on the weight of the reactants (lignin-cellulose, polyol and polyisocyanate) are mixed and the resultant mixture is reacted thereby producing a polyurethane-lignin cellulose foamed product; the foamed product is then emerged in water for 1 to 3 hours thereby curing the water-binding agent.
  • reactants lignin-cellulose, polyol and polyisocyanate
  • 1 to 3 parts by weight of the lignin-cellulose resinous product, 1 to 3 parts by weight of a polyol, 1 to 3 parts by weight of an alkali metal silicate such as sodium and potassium silicate, up to 5% by weight of an emulsifying agent and up to 10% by weight of an amine catalyst are mixed to form an emulsion then mixed with a mixture of 3 parts by weight of an organic polyisocyanate or polyisothiocyanate, up to 50% by weight of an inert, volatile blowing agent and up to 20% by weight of a foam stabilizer, percentage based on the weight of the reactants (lignin-cellulose resinous product polyol, polyisocyanate and alkali metal silicate), the resultant mixture is allowed to react at 20o C to 80° C thereby producing a poly(urethane- lignin-cellulose-alkali metal silicate) foam.
  • an alkali metal silicate such as sodium and potassium silicate
  • 1 to 3 parts by weight of the lignin-cellulose resinous product as produced in the process of this invention 3 parts by weight of an isocyanate-terminated polyurethane prepolymer, up to 10% by weight of amine catalyst, up to 20% by weight of a foam stabilizer, up to 50% by weight of an inert volatile blowing agent, up to 100% by weight of a curing agent and up to 3 parts by weight of a polyol are mixed; the resultant mixture is allowed to react thereby producing a polyurethane solid or foamed plaster.
  • Readily volatile blowing agents e.g., dichlorodifluoromethane, trichlorofluoromethane, butane, isobutylene or vinyl chloride, may be used to produce celluloar solid products in this invention.
  • the liquid reaction mixtures can be expanded into a foam by the introduction of gases, optionally under pressure, such as air, methane, CF 4 , noble gases ahd H 2 O 2 , the resulting foam being introduced into the required mold and hardened therein.
  • the resultant foam may optionally contain foam stabilizers such as surfactants, foam formers, emulsifiers and, if desired, other organic or inorganic fillers or diluents may initially be converted by blowing gas into a foam and the resulting foam subsequently mixed in a mixer with the other components, the resulting mixture being allowed to harden.
  • foam stabilizers such as surfactants, foam formers, emulsifiers and, if desired, other organic or inorganic fillers or diluents may initially be converted by blowing gas into a foam and the resulting foam subsequently mixed in a mixer with the other components, the resulting mixture being allowed to harden.
  • foam stabilizers such as surfactants, foam formers, emulsifiers and, if desired, other organic or inorganic fillers or diluents may initially be converted by blowing gas into a foam and the resulting foam subsequently mixed in a mixer with the other components, the resulting mixture being allowed to harden.
  • the foams obtainable in this way can be used either in their dry or their moist form if desired after a compacting or tempering process, optionally carried out under pressure, as insulating materials, cavity fillings, packaging materials, building materials, etc. They can also be used in the form of sandwich elements, for example, with metal covering layers, in house, vehicle and aircraft construction.
  • foaming reaction mixtures for example, expanded clay, expanded glass, wood, popcorn, cork, hollow beads of plastics, for example, vinyl chloride polymers, polyethylene, styrene polymers or foam particles thereof or even, for example, polysulphone, polyepoxide, polyurethane, ureaformaldehyde, phenol formaldehyde, polyimide polymers, urea-silicate-formaldehyde polymers, phenol-silicate-formaldehyde, epoxy silicate polymers, polyisocyanate silicate polymers, polyurethane silicate polymers or the reaction mixture may be allowed to foam through interstitial spaced particles in packed volumes of these particles and, in this way, to produce insulating materials. Combinations of expanded clay, glass or slate with the reaction mixture, according to the invention, are especially preferred.
  • the initial liquid mixture formed can be used not only for producing uniform foams or non-uniform foams containing foamed or unfoamed fillers, but it can also be used to foam through any given webs, woven fabrics, lattices, structural elements or other permeable structures of foamed materials, resulting in the formation of composite foams with special properties, for example, favorable flame behavior, which may optionally be directly used as structural elements in the building, furniture or vehicle and aircraft industries.
  • the cellular solid products (foams) according to the invention can be added to soil in the form of crumbs, optionally in admixtures with fertilizers and plant-protection agents, in order to improve its agrarian consistency.
  • the hardened foams obtained by the process according to the invention can show considerable porosity after drying, they are suitable for use as drying agents because they can absorb water; however, they can also be charged with active substances or used as catalyst supports or filters and absorbents.
  • the foams can be subsequently lacquered, metallized, coated, laminated, galvanized, subjected to vapor deposition, bonded or flocked in either their moist or dry form or in impregnated form.
  • the moldings can be further processed in their moist or dried form, for example, by sawing, milling, drilling, planing, polishing and other machining techniques.
  • the optionally filled molding can be further modified in their properties by thermal after-treatment, oxidation processes, hot-pressing, sintering processes or surface melting or other consolidation processes.
  • Suitable mold materials include inorganic and/or organic foamed or unfoamed materials such as metals, for example, iron, nickel, fine steel, lacquered or, for example, teflon-coated aluminum, porcelain, glass, wood, plastics such as PVC, polyethylene, epoxide resins, ABS, polycarbonate, etc.
  • Fillers in the form of particulate or powdered materials can be additionally incorporated into the liquid mixtures of the foamable reactants for a number of applications.
  • Suitable fillers include solid inorganic or organic substances, for example, in the form of powders, granulate, wire, fibers, dumb bells, crystallites, spirals, rods, beads, hollow beads, foam particles, webs, pieces of woven fabric, knit fabrics, ribbons, pieces of film, etc., for example, of dolomite, chalk, alumina, asbestos, basic silicas, sand, talcum, iron oxide, aluminum oxide and oxide hydrate, zeolites, calcium silicates, basalt wool or powder, glass fibers, C-fibers, .graphite, carbon black, A1-, Fe-, Cu-, Ag-powder, molybdenum sulphite, steel wool, bronze or copper cloth, silicon powder, expanded clay particles, hollow glass beads, glass powder, lava and pumice particles, wood chips, sawdust, cork, cotton, straw, jute, sisal, hemp, flax, rayon, popcorn, coke, particles of filled or unfilled, foamed or unf
  • suitable organic polymers the following, which can be present, for example, in the form of powders, granulate, foam particles, beads, hollow beads, foamable or unfoamed particles, fibers, ribbons, woven fabrics, webs, etc., are mentioned purely by way of examples: polystyrene, polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polyisoprene, polytetrafluoroethylene, aliphatic and aromatic polyesters, melamine-urea or phenol resins, polyacetal resins, polyepoxides, polyhydantoins, polyurea, polyethers, polyurethanes, polyimides, polyamides, polysulphones, polycarbonates, and, of course, any copolymers as well.
  • Inorganic fillers are preferred.
  • the composite materials according to the invention can be filled with considerable quantities of fillers without losing their valuable property spectrum.
  • the amount of fillers can exceed the amount of the reactants.
  • the foamed products of the present invention act as a binder for such fillers.
  • the production of the cellular solid products according to the invention is carried out by mixing the reactants in one or more stages in a continuously- or intermittently-operated mixing apparatus and then allowing the resulting mixture to foam and solidify, usually outside the mixing apparatus in molds, or on suitable materials.
  • the reaction temperature required for this which may be from 0o C to 200° C and preferably from 20° C to 160o C, may either be achieved by heating one or more of the reactants before the mixing process or by heating the mixing apparatus itself or, alternatively, by heating the reaction mixture after the components have been mixed. Combinations of these or other methods of adjusting the reaction temperature may, of course, also be employed. In most cases, sufficient heat is evolved during the reaction to enable the reaction temperature to rise to values above 50o C after the reaction or foaming has begun.
  • the process according to the invention is suitable for in situ foaming on the building site.
  • Any hollow forms obtained by means of shuttering in the conventional way may be filled up and used for foaming in this way.
  • the lignin-cellulose resinous product as produced in this invention may be pre-reacted with an amino compound and an aldehyde, at a pH of 7 to 12, to produce a li ⁇ uid alkali cellulose-amino-aldehyde, then placed in a mixing chamber, optionally adding a blowing agent, emulsfier, foam stabilizer, filler, flame-retardant and other additives, then rapidly mixed with an acid compound and then pumped or blown by compressed air into a mold such as a wall, ceiling, etc., while expanding, thereby producing a cellular solid product, useful for sound and thermal insulation.
  • the foaming components may also be pumped into a large mold to expand and harden into a cellular product.
  • the cellular product may be sawed into slabs and used for insulation in houses, boats, vehicles, airplanes, etc.
  • the cellular product may also be chopped by a suitable machine into particles and poured or blown into places such as ceilings, walls, etc., and used for thermal and sound insulation.
  • the cellular product may also be used as a molding powder and molded into useful products by heat and pressure in a mold.
  • the lignin-cellulose resinous product as produced in this invention may be pre-reacted with a phenol compound and an aldehyde, at a pH of 7 to 12, to produce a liquid polymer.
  • This liquid polymer may be foamed in the same manner as the amino-aldehyde-lignin-cellulose polymers and may be used for the same purposes, sound and thermal insulation, molding powder and in the production of pains, varnishes, adhesives, etc.
  • the liquid phenoplast lignin-cellulose polymer may be poured into a mold, then heated for 1 to 6 hours, thereby producing a tough, solid, useful product.
  • the alkali cellulose polymer as produced in this invention may be pre-reacted with a phenol compound, an amino and an aldehyde compound at a pH of 7 to 12, to produce a li ⁇ uid resin.
  • This liquid resin may be poured into a mold, then heated to 70o C to 100o C for 1 to 6 hours, thereby producing a tough, solid, useful product.
  • This liquid resin may also be foamed on the job by adding the liquid resin and an acid compound (catalyst) simultaneously to a mixing chamber, then rapidly pumping or using air pressure to transfer the foaming mixture into a mold such as walls, ceilings, etc., where it rapidly sets within a few seconds to several minutes into a tough, rigid, somewhat elastic, cellular solid product, optionally containing blowing agent, emulsifier, foam stabilizer, filler, flame-retardant agents and other additives.
  • the product has good sound and thermal qualities, good flame-retardant properties and good dimensional stability.
  • the phenoplast-lignin-cellulose-aminoplast resins may be used as molding powder and molded by heat and pressure into useful objects.
  • the phenoplast-lignin-cellulose-aminoplast resin may be foamed into large slabs, then sawed into various sizes and thicknesses or broken into small particles and used for thermal and sound insulation in houses, buildings, vehicles and aircrafts; these large slabs of foam may be sawed into various thicknesses and widths, then a moisture barrier such as aluminum foil may be applied by the use of an adhesive to produce an insulation material that has excellent flame-resistant properties, good strength and excellent thermal- and sound-insulation qualities.
  • the process according to the invention to produce the polyisocyanate lignin-cellulose foam, polyurethane lignin cellulose foam and polyurethane-silicate-lignin-cellulose foam is particularly suitable, however, for in situ foaming on the building site.
  • Any hollow molds normally produced by shuttering in forms can be obtained by casting and foaming.
  • the reaction mixture optionally containing a blowing agent, emulsifier, foam stabilizer, filler, flame-retardant agent, diluents, deodorants, coloring agents and other agents, produced by adding the components simultaneously to a mixing apparatus, is immediately pumped or sprayed by compressed air into a mold, e.g., walls, ceilings, cold or heated relief molds, solid molds, hollow-molds, etc., where it may be left to harden.
  • a mold e.g., walls, ceilings, cold or heated relief molds, solid molds, hollow-molds, etc.
  • the foaming reaction mixture may also be forced, cast or injection molded into cold or heated molds, then hardened, optionally under pressure and at room temperature or at temperatures up to 200o C, optionally using a centrifugal casting process.
  • reinforcing elements in the form of inorganic and/or organic or metal wires, fibers, non-woven webs, foams, fabrics, supporting structures, etc. may be incorporated in the foaming mixture. This may be achieved, for example, by the fibrous-web-impregnation process or by processes in which the reaction mixtures and reinforcing fibers are together applied to the mold, for example, by means of a spray apparatus.
  • the molded products obtainable in this way may be used as building elements, e.g., in the form of optionally foamed sandwich elements which may be used directly or subsequently laminated with metal, glass, plastics, etc.
  • the fire characteristics of the material are good, but are improved by the addition of flame-retardant agents and also by the addition of the oxidated silicon compounds.
  • the products may be used as hollow bodies, e.g., as containers for goods which are required to be kept moist or cool, or they may be used as filter materials or exchangers, as catalyst carriers or carrier of other active substances, as decoration elements, shock-resistant packaging, furniture components and cavity fillings. They may also be used in production of molds for metal casting and in model building.
  • the cellular products may also be produced by pouring the components into a mold, then mixing well, after which the mixture expands, then hardens in the mold.
  • the mold may be in the form of a large slab so that it can be sawed into various sizes, shapes and thicknesses as desired.
  • the reaction mixtures may also be foamed up and hardened while the form of droplets or may be dispersed, e.g., in petroleum hydrocarbons or while they are under condition of free fall. Foam beads are obtained in this way.
  • the foamed products produced by these methods may also be added in a crumbly form to soil, optionally with the addition of fertilizers and plant-protective agents so as to improve the agricultural consistency of the soil.
  • Foams which have ahigh water content may be used as substrates for the propagation of seedlings, shoots and plants or for cut flowers.
  • the mixtures may be sprayed on terrain which is impassible or too loose, such as dunes or marshes, to strengthen such terrain so that it will be firm enough to walk on within a short time, and will be protected against erosion.
  • the foaming mixtures may also be used underground in caves, mines, tunnels, etc., by spraying the foaming mixture onto wire mesh, fiberglass cloth, woven fabrics or directly on the walls, to produce protective layers to prvent accidents.
  • the lignin-cellulose resinous product, poly(aldehyde lignin-cellulose) resinous product, poly(aminoplast-lignin-cellulose) resinous product, poly(phenoplast lignin-cellulose) and poly(aminoplast-lignin-cellulose phenoplast) resinous produced may use as a thermosetting resinous adhesive useful particularly as plywood for lumbar laminating adhesive.
  • the adhesive may be cured by heat (250° C to 300° C) and pressure (110 to 260 psi) .
  • the adhesive resinous products will also cure by the presence of an alkali or acetic catalyst or by using hexamethylene or paraformaldehyde.
  • poly(polyisocyanate-lignin-cellulose) polyurethane lignin cellulose, polyurethane lignin-cellulose silicate and poly(polyisocyanate lignin-cellulose silicate) cellular products are soluble in organic solvents and may be utilized as paints, varnishes, adhesives, fillers, caulking material, etc.
  • the object of the present invention is to provide a novel process to produce lignin-cellulose resinous products, carbohydrates and CO 2 from cellulose-containing plants. Another object is to produce novel lignin-cellulose resinous products which are highly reactive. Still another object is to product carbohydrates which can be fermented to produce ethanol. Another object is to produce novel poly(furfuryl alcohol-lignin-cellulose) resinous products. Still another object is to produce lignin-cellulose resinous product which will react chemically with aldehydes to produce novel po aldehyde lignin-cellulose) resinous product and foams.
  • Another object is to produce novel lignin-cellulose polymers that will react with aldehydes and amino compounds to produce novel poly(aminoplast lignin-cellulose) resins and foams. Another object is to produce lignin-cellulose polymers that will react with aldehyde compounds and phenol compounds to produce novel poly (phenoplast lignin-cellulose) resins and foams. Another object is to produce lignin cellulose polymers that will react with polyisocyanate compounds and polyurethane prepolymers to produce novel poly(polyisocyanate lignin-cellulose) and poly(urethane lignin-cellulose) resins and cellular products. Another object is to produce lignin-cellulose polymers that will react with polyurethane prepolymers and oxidated silicon compounds to produce novel poly(urethane-lignin-cellulose-silicate) resins and cellular solid products.
  • the lignin-cellulose resinous product is recovered by filtration, then ground into a powder, washed with water to remove any salt, then dried.
  • the lignin-cellulose resinous product soften at about 120o C and may be molded into useful products by heat and pressure.
  • wood may be used in place of fir such as pine, redwood, cedar, oak, spruce, gum, hemlock, walnut, hickory, eucalyptus, birch, poplar, beech, maple, mahogany, aspen, ash, cypress, elm, cherry, sycamore and mixtures thereof.
  • salt forming compounds may be used in place of acetic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, propionic acid, acetic acid chloride, maleic acid, glutaric acid anhydride, oxalic acid, potassium hydrogen sulfide, sodium dihydrogen phosphate and mixtures thereof.
  • cellulose products may be used in place of cotton, such as wood pulp with lignin removed by soda process, wood pulp with lignin removed by the acid process, wood pulp from waste paper and mixtures thereof.
  • corn cob particles About 2 parts by weight of corn cob particles is added to sodium hydroxide at 150o to 220o C while agitating at ambient pressure for 5 to 60 minutes thereby producing a water soluble broken down alkali metal cellulose-plant polymer, dark brown in color. Dilute hydrochloric acid is added to said polymer until the pH is 5 to 6.5 thereby producing a lignin-cellulose resinous product, CO 2 and carbohydrates.
  • dry cellulose containing plant particles may be used in place of corn cobs, such as corn stalks, seaweed, cotton stalks, rice straw, wheat straw, oat straw, barley straw, soybean stalks, cane sugar stalks, pea vines, bean vines, sugar beet waste, sorghum stalks, tobacco stalks, maize stalks, buckwheat straw, weeds, bushes, grass, algae, humus, peat and mixtures thereof.
  • lignin-cellulose resinous polymer as produced in Example 1 About 4 parts by weight of the lignin-cellulose resinous polymer as produced in Example 1 are mixed with 3 parts by weight of an aqueous solution containing 37% formaldehyde, then adjusting the pH to about 8 with sodium carbonate, then heating the mixture to 70o C to 100o C while agitating for 30 to 120 minutes, thereby producing a poly(formaldehyde lignin-cellulose) resinous product.
  • lignin-cellulose resinous product About 4 parts by weight of the lignin-cellulose resinous product are mixed with 2 parts by weight of furfural then 0.5 parts by weight of hydrochloric acid is added and thoroughly mixed, then poured into a mold of a useful product thereby producing a poly(furfural-lignin-cellulose) resinous product.
  • lignin-cellulose resinous product About 4 parts by weight of the lignin-cellulose resinous product are mixed with 3 parts by weight of furfuryl alcohol then 0.5 parts by weight of 6 normal sulfuric acid is added and thoroughly mixed then poured into a mold of a useful product, thereby producing a poly (furfuryl alcohol-lignin-cellulose) resinous product.
  • lignin-cellulose resinous product About 2 parts by weight of the lignin-cellulose resinous product and 2 parts by weight of crotonaldehyde are mixed then an aqueous solution of sodium hydroxide is added until the pH is 8 to 10. The mixture is agitated at a temperature between 20o C to 100° C for 30 to 120 minutes, thereby producing a poly(crotonaldehyde lignin-cellulose) resinous product.
  • aldehydes may be used in place of crotonaldehyde such as formaldehyde, acetaldehyde, paraformaldehyde, propionic aldehyde, furfural, acrolein, benzaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanals and mixtures thereof.
  • aldehydes may be used in place of formaldehyde such as crotonaldehyde, acetaldehyde, propionic aldehyde, furfural, acrolein, paraformaldehyde, benzaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanals and mixtures thereof.
  • formaldehyde such as crotonaldehyde, acetaldehyde, propionic aldehyde, furfural, acrolein, paraformaldehyde, benzaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanals and mixtures thereof.
  • amino compounds may be used in place of urea such as thiourea, alkyl ureas, dicyandiamide melamine, polyamines, aniline and mixtures thereof.
  • lignin-cellulose resinous products as produced in Claim 4
  • about 4 parts by weight of aqueous solution containing 37% by weight of formaldehyde and 3 parts by weight of urea are mixed thoroughly, then dilute hydrochloric acid is added until the pH is about 5 to 6 and the mixture rapidly solidify thereby producing a poly(aldehyde amino lignin-cellulose) resinous product.
  • lignin-cellulose resinous product About 4 parts by weight of lignin-cellulose resinous product, 4 parts by weight of an aqueous solution containing 37% by weight of formaldehyde and 5 parts by weight of urea are mixed, then sodium carbonate is added until the pH is about 8.
  • the mixture is then heated at about 70o C for 10 to 20 minutes; about 2 parts by weight of trichlorotrifluoroethane is added and thoroughly mixed with the mixture, then hydrochloric acid is rapidly added until the pH is about 5 to 6 while rapidly agitating until the mixture begins to expand. It expands 5 to 12 times its original volume thereby producing a poly(aldehyde amino lignin-cellulose) foam.
  • lignin-cellulose resinous product as produced in Example 6, 3 parts by weight of an aqueous solution containing 37% formaldehyde and stifficient ammonium hydroxide to produce a pH of 8 to 10 and 3 parts by weight of phenol are mixed, then heated to 70° to 100° C while agitating for 30 to 120 minutes thereby producing a poly(aldehyde phenol lignin-cellulose) resinous product.
  • phenol compounds may be used in place of phenol such as cresol, creosote, cresylic acid, resorcinol, Bisphenol A, cashew nut shell liquid, 2, 6-dimethylphenol, p-tert-butyl phenol and mixtures thereof.
  • aldehydes may be used in place of formaldehyde such as acetaldehyde, propionic aldehyde, furfural, crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde, pentanals, hexanals, heptanals, octanals, and mixtures thereof.
  • lignin-cellulose resinous product as produced in Example 1, 2 parts by weight of cresol, 2 parts by weight of furfural are thoroughly mixed, then sufficient hydrochloric acid is added until the pH is about 5 to 6, as tested in water, thereby producing a poly(aldehyde phenol lignin-cellulose) resinous product.
  • lignin-cellulose resinous product as produced in Example 2, about 1 part by weight of resorcinol, 2 parts by weight of phenol and 3 parts by weight of an aqueous solution containing 37% formaldehyde .are mixed, then sodium hydroxide is added until the pH is 8 to 10 then heated to 70° to 100° C while agitating for 30 to 120 minutes thereby producing a thermoplastic poly(aldehyde phenol lignin-cellulose) resinous product.
  • This resinous product may be used as an adhesive in manufactory of plywood.
  • lignin-cellulose resinous product as produced in Example 1, about 2 parts by weight of phenol and 0.5 parts by weight of an aqueous solution of containing 37% by weight of formaldehyde are mixed then hydrochloric acid is added until the pH is 5 to 6 then the mixture is heated to 70° C to 100° C while agitating for 30 to 120 minutes, thereby producing a themoplastic poly(alde hyde phenol lignin-cellulose) resinous product.
  • the resinous product is ground into a molding powder then mixed with fillers, pigments and hexamethylene tetramine.
  • the molding powder mixture is placed in a mold then cured by heat (250° to 300° F) and pressure (110 to 260 psi). Paraformaldehyde may be used in place of hexamethylene tetramine.
  • lignin-cellulose resinous product as produced in Example 6, 4 parts by weight of urea, 1 part by weight of cresylic acid and 4 parts by weight of an aqueous solution containing 37% by weight of formaldehyde are thoroughly mixed, thsmfoamed with the compressed air, then hydrochloric acid is added in sufficient amount to produce a pH of 5 to 6; the mixture rapidly solidifies thereby producing a poly(aldehyde amino phenol lignin-cellulose) foam.
  • thermosetting resin produced by reacting phenol with formaldehyde in the ratio of 1:1.5 in the presence of an alkaline catalyst is mixed with about equal parts by weight of lignin-cellulose resinous product as produced in Example 1 then cured by heat (250o to 300o F) and pressure (110 to 260 psi) between layers of wood veneer to produce a plywood panel.
  • thermosetting liquid resin produced by reacting phenol with formaldehyde in the ratio of 1:0.8 in the presence of an acid catalyst is mixed with about equal parts by weight of lignin-cellulose resinous product as produced in Example 2. Then about 100 parts by weight of this mixture is mixed with 5 parts by weight of paraformaldehyde and 5 parts by weight of hexamethylene tetraamine and applied to layers of wood veneer then cured by heat (250o to 300o F) and pressure (110 to 260 psi) for 10 to 60 minutes.
  • Example 2 About 2 parts by weight of the lignin-cellulose resinous product produced in Example 1 is ground into a powder, washed, filtered and dried, then mixed with 4 parts by weight of tolylene diisocyanate ("TDI") then heated to 20° C to 70° C for 10 to 60 minutes thereby producing a poly(polyisocyanate lignin-cellulose) polymer.
  • TKI tolylene diisocyanate
  • Example 22 About 100 parts by weight of the poly(polyisocyanate lignin- cellulose) prepolymer and a curing agent listed below is thoroughly mixed with the prepolymer at a temperature between 18o to 40o C thereby producing a rigid poly(polyisocyanate lignin-cellulose) foam.
  • lignin-cellulose resinous product as produced in Example 2 and 3 parts by weight of MDI ("PAPI 27" produced by Upjohn) are mixed then agitated at a temperature between 20o C to 70o C for 10 to 60 minutes thereby producing a poly(polyisocyanate lignin-cellulose) prepolymer.
  • the prepolymer is then thoroughly mixed with 0.4 parts by weight of water containing 20% dimethylethanol amino thereby producing a brown rigid poly(polyisocyanate lignin- cellulose) foam.
  • lignin-cellulose resinous product in the form of a powder, 3 parts by weight of tolylene diisocyanate ("TDI") , 1 part by weight of trichlorotrifluoroethane, 0.1 part by weight of triethylenediamine and parts by weight of polyol listed below are thoroughly mixed and the mixture expands 5 to 12 times its original volume to produce a rigid polyurethane lignin cellulose foam.
  • TDI tolylene diisocyanate
  • Example 24 is modified to wherein 2 parts by weight of Portland Cement is added to both the polypropylene glycol and TDI thereby producing a rigid polyurethane-lignin-cellulose foam. The foam is then emerged in water for 1 to 3 hours to cure the unreacted cement.
  • Other water-binding agents may be used in place of hydraulic cement such as burnt lime, gypsum and synthetic anhydrite.
  • a powdered lignin-cellulose res us product 2 parts by weight polyethylene glycol (mol. wt. 600), 4 parts by weight of sodium metasilicate pentahydrate and 0.1 part by weight of sodium doctyl sulfosuccinate are mixed at about 70o C to form an emulsion then 0.1 parts by weight of p-aminobenzoic acid and 0.1 parts by weight of triethylamine are mixed in thoroughly. The mixture is then thoroughly mixed with 5 parts by weight ot tolylene diisocyanate ("TDI”) and 1 part by weight of trichlorotrifluoroethane. The mixture expands 8 to 12 times its original volume to produce a semi-rigid poly (urethane lignin-cellulose alkali metal silicate) foam.
  • TDI ot tolylene diisocyanate
  • Example 30 Claim 29 is modified by adding 1 part by weight of sodium metasilicate pentahydrate with lignin-cellulose resinous product.
  • Example 31 Claim 29 is modified by adding 3 parts by weight of Portland cement to the isocyanate-terminated polyurethane prepolymer.

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Abstract

Des plantes contenant de la cellulose sont decomposees par melange avec un hydroxide de metal alcalin, puis chauffage a 150 -220 C sous agitation pendant 5 a 60 minutes, pour obtenir un polymere vegetal hydrolyse contenant de la cellulose et un metal alcalin, lequel est melange a un compose acide jusqu'a ce que le pH soit compris entre 5 et 7 donnant ainsi un produit resineux de lignine-cellulose et un melange d'hydrates de carbone.
PCT/US1980/001092 1980-05-12 1980-08-25 Production de resines de lignine-cellulose et d'hydrates de carbone WO1981003332A1 (fr)

Priority Applications (1)

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AU63940/80A AU6394080A (en) 1980-05-12 1980-08-25 Production of lignin-cellulose resins and carbohydrate

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US14917880A 1980-05-12 1980-05-12
US149178 1980-05-12

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WO1981003332A1 true WO1981003332A1 (fr) 1981-11-26

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EP (1) EP0052097A1 (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342781A2 (fr) * 1988-05-16 1989-11-23 Director-General Of The Agency Of Industrial Science And Technology Polyuréthane et son procédé de préparation
WO2014046826A1 (fr) * 2012-09-20 2014-03-27 Graftech International Holdings Inc. Fibres de carbone dérivées de lignine
AT513670A1 (de) * 2012-11-26 2014-06-15 Annikki Gmbh Verfahren zur Herstellung von Phenol-Formaldehyd-Harz-analogen Polymeren
US9758905B2 (en) 2012-11-16 2017-09-12 Graftech International Holdings Inc. Process of making carbon fibers derived from lignin/carbon residue
US10011492B2 (en) 2013-09-05 2018-07-03 Graftech International Holdings Inc. Carbon products derived from lignin/carbon residue

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EP0342781A2 (fr) * 1988-05-16 1989-11-23 Director-General Of The Agency Of Industrial Science And Technology Polyuréthane et son procédé de préparation
EP0342781A3 (en) * 1988-05-16 1990-11-07 Director-General Of Agency Of Industrial Science And Technology New polyurethane and process for preparing same
WO2014046826A1 (fr) * 2012-09-20 2014-03-27 Graftech International Holdings Inc. Fibres de carbone dérivées de lignine
CN104797751A (zh) * 2012-09-20 2015-07-22 格拉弗技术国际控股有限公司 衍生自木质素的碳纤维
US9683313B2 (en) 2012-09-20 2017-06-20 Graftech International Holdings Inc. Method of making carbon fibers from lignin
US9758905B2 (en) 2012-11-16 2017-09-12 Graftech International Holdings Inc. Process of making carbon fibers derived from lignin/carbon residue
AT513670A1 (de) * 2012-11-26 2014-06-15 Annikki Gmbh Verfahren zur Herstellung von Phenol-Formaldehyd-Harz-analogen Polymeren
US10011492B2 (en) 2013-09-05 2018-07-03 Graftech International Holdings Inc. Carbon products derived from lignin/carbon residue

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