TECHNICAL FIELD

Small particles of cellulose-containing plants are mixed with an alkali mεtal hydroxide, such as lye flakes, in the ratio of about 2 parts by weight of the plant to 1 to 3 parts by weight of the alkali metal hydroxide, then heated to 150 C to 220 C for 5 to 60 minutes while agitating until the plant particles soften or melt, thereby producing broken-down cellulose polymers in the form of dark brown particles cr powder.

DISCLOSURE OF INVENTION

This invention relates to a novel and economical process to break down particles of cellulose-containing plants into smaller polymers and compo ^u nds which ere highly *-eacti' ^r e chemi¬ cally and a-*~ soluable in water an or co~cr. cc-aπic solvents.

The p-ocess in this in'ention differs from the process commonly kno',.*n in the arts to produce alkali metal cellulose by heating the cellulose in a concentrated aqueous solution of the alkali metal hydroxide to break down the cellulose polymers; the alkali metal cellulose produced is not solvable in vrater and Trust be reacted with c rbo dis lfi e before it is water soluable.

OMPI

In the process of this invention, aqueous solutions are not used and a much higher temperature is necessary to break down the cellulose polymers in plants in order for it to be water soluable. It is not necessary to remove the lignin for wood in the process of this invention- When an organic cr inorganic acid is added to the broken-dovm alkali metal cellulose polymer, carbon dioxide is given off. The dark brown alkali metal cell¬ ulose polymer is usually converted to a cream color a ter the cellulose is reacted with other organic reactants, especially in an acetic medium..

When wood is used as the cellulose-containing plant, the usual lignin-cellulose bond is not broken in most z ^~ the cases, but the molecules of cellulose are broken down int3 smaller mole¬ cules which are water soluable and highly reactive c emically, especially with aldehydes, furan compounds, polyisocyanate com¬ pounds and polyurethane prepolymers.

The broken-down polymers of cellulose-containi-'.r plants are commercially useful polymers. The alkali celluloss of cellulose- containing plants is highly reactive. It will prc _ce useful re¬ sins by reacting with aldehydes, ketor.es, isocyanat s, ^τr inyl ace¬ tate acrylic acid monomers, polyfunctional alkylatlr-g agents, monofunctional alkylating agents, aldehydes and >=--3ls, aldehydes

OMPI

^:

and arπino compounds, vinyl acetate with other --inyl monomers, acrylic acid compounds with other vinyl monomers, epihalohydrins with pplyamines, oxidated silicon compounds, sulfur, silicon halides, organic polyhalides and polyamines, furfuryl alcohol, compounds which contain halogen atoms capable of being ςu ter- nized or R-SO^-groups, epoxide compounds and mixtures thereof. The aqueous solution of the alkali metal cellulose poly¬ mers of cellulose-containing plants may be used commercially to react with polyisocyanate and isocyanate-termi ated polyirethane prepolymers and isocyanate-terminated polyurethane silicate pre- polymers. They may be polymerized with organic aldehydes, fur¬ furyl alcohol, epihalohydrins and polyaminε organic polyhalide ccrπp ur-ds, organic epichiorohydrin compounds and a poiyamine, haloh drins, ketones, organic epoxides, acrylic compounds, vinyl acetate, organic halides, organic polyhalides, crganic acid sul- fates, organic poly(acid sulfates) , organic nitrates, organic poly- nitrates, organic acid phosphates, organic pol Cacid phosphates), organic bicarbonate, organic poly(bicarbonate) compounds contain¬ ing radicals, organic compounds containing formate radicals, or¬ ganic compounds containing poly(formate) radicals, organic com¬ pounds containing acetate, propionate, laurate, oleate, stearate, ox-late, acid malonate, acid tartrate, acid citrate radical and mixtures thereof.

OMPI Λ, WIPO _Λ

The water-soluable alkali metal polymer: may be precipi¬ tated by the addition of a salt—forming compound,, such, as an organic or inorganic acid.. The. water- is filtered off.. The water contains 5% to 30% by weight of plant polymers and, in the case of wood, some lignin is present. The degraded cellu- _ lose polymers are precipitated as dark brow to black fine particles vhich are soluable in acetic acid, alcohols, dilute alkali hydroxide solutions and other organic solvents. The broken-down cellulose polymers may be chemically reacted with isocyanate compounds, polyisocyanate compounds, polythiciso- cyanate compounds, silicon halides, polycarboxyl acids and their corresponding anhydride _r epoxides, aldehydes, ketcnes, furfuryl alcohol, epihalohydrins and mixtures thereof.

The water-soluable broken-down cellulose polymers and lignin are soluable in acetic and basic aqueous solutions. They may be used in the aq^eous solution to produce resins by reacting with furfural, furfuryl alccriol, aldehyde and an amino compound, aldehyde and a phenol compound, aldehydes, ketones, epoxides and poiyamines, roiyhalide organic compounds and polyamines, isocya- r.ates and mixtures thereof. The salt may be removed by -washing the resins with 'water and filtering. The water-soluable broken- dOwT. cellulose polymers may be recovered by evaporating the -water., the-- extracting the polymers from the salt by using an organic

-5-

solvenfc, and then evaporating the organic solvent. The tan- colored cellulose polymer may be used in .the production of poly- urethane resins and* foams _r phenoplast, aminoplasts, aldehyde cel¬ lulose resins, ketone cellulose resins, furfuryl alcohol-cellu¬ lose resins, cellulose silicone polymers and as a filler in — paints, varnishes, organic resins, etc.

When desireable, a higher percentage of alkali metal cellu¬ lose polymers may be produced, which are not water soluable, by regulating the temperature and the length of time the alkali metal hydroxide and cellulose-containing plants are heated. These polymers are highly reactive, as previously discussed.

Any s-vitable cellulose-containing plant or the products of cellulose-containing plants v/hich 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 _τ elm, chestnut, hickory, locust, sycamore, tulip, t pelo, butternut, apple, alder, magnolia, dogwood, catalpa, box¬ wood, crabwopd, mahogany, greenheart, lancewood, letterwσod, mora,

-6-

prima- vera, purpleheart, rosewood, teak, satinwood, mangrove, wattle, orange, lemon, logwood,, fustic, osage orange, sappanwood, Brazilv.'ood, barwσσd,, camwood, sandalv/ood, rubber, gutta, mesquite, an shrubs, e.g., oleander, cypress, junipers, acanthus, pyra— cantha, ligustrum, lantana, bougainvillea, azalea, feijoa, ilex,— fuscia, hibiscus, datura, holly, hydrangea, jasmine, eucalyptus, cottoneaster, xylosma, rhododendron, castor bean, eugenia, euony- mus, fatshedera, aralia, etc., and agricultural plants, e.g., cotton, cotton stalks, corn stalks, corn cobs, wheat straw, oat straw, rice straw, cane sugar (bagasse), soybean stalks, peanut plants, pea vines, sugar beet waste, sorghum stalks, tobacco stalks, maize stalks, barley straw, buckrwheat straw, quinoa stalks, cassava, potato plants, legume vines and stalks, vegetable inedible portion, etc., weeds, grasses,- ines, kelp, flowers and algae. ^'• Jood fibers and cotton fibers are the preferred cellulose-con¬ taining materials. The waste products of agricultural plants v/hich contain cellulose may be air-dried, then ground into small particles and used in this invention. Conr-ner ial waste products containing cellulose, e.g., paper, cotton cloths, bagasse wall- board, 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 de¬ composed, such as humus, peat and certain soft brow-n coal, may be used in this invention.

Other products of cellulose-containing plants may be re¬ covered in the process of this invention such as waxes, gums, oils, sugars, v/ood alcohol, agar, rosin, turpentine, resins, rub¬ ber latex, dyes, etc.

Any suitable aldehyde may be used in this invention, such as formaldehyde, acetaldehyde, butyl aldehyde, chloral, .acrolein furfural, benzaldehyde, crotonaldehyde, propionaldehyde, penta- nals, hexanals, heptanals, octanals and their simple substitu¬ tion 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 aε urea, thiourea, al yl-substituted t iourea, alkyl- substituted ureas, melamine, aniline, quanidine, saccharin, dicyandiamide, benzene sulfonarides, toluene sulfonamide, ali¬ phatic and aromatic polyamines and mixtures thereof. Urea is the preferred a-mϊno compound, and formaldehyde is the preferred aldehyde v/hen used with the a-o- -io compound.

Any suitable phenol compound may be used in this invention such as phenol, p-cresol, o-cresol, m-crescl, cresylic acid,

-8- .- ^' . ^"

xylenolds _y resorcinol, cashew nut shell liquids, anacordol,, p—tert- butyl phenol, Bisphenol A, creosote oil, 2,6-dimethylphεnαI and mixtures thereof _* Phenol-is the preferred phenol compound and formaldehyde is the preferred aldehyde v/hen used with a phenol compound. _

Any suitable mixture of the amino compounds and phenol com¬ pounds with an aldehyde may be used in this invention.

Any suitable acid compound, inorganic or organic, may be used for salt formation, including those v/hich 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, tar- taric acid, oxalic acid, phthalic acid, triiπellitic 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 hydro¬ chloric, fluoroboric acid, amidos lphonic 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 alkali metal cellulose polymer to produce a salt and

OM Λ. IP

also release CO vhich expands the cellulose polymer into a cellular solid product. The acid compounds may also be used as a catalyst in the reactions to produce foamed aminopl s - cellulose products, foamed phenoplast-cellulose products and arainoplast-cellulose-phenoplast foamed products. These acid — compounds may also be used in the production of polyurethane- cellulose cellular solid products to react with the alkali metal atoms to form a salt. The acid compounds may be used to precipitate ^' the alkali metal cellulose from an aqueous solu¬ tion.

Any suitable oxidated silicon compound may be xzised in this invention such as silica, e.g., hydrated silica, silico- for ic acid, silica sol, etc., alkali metal silicates, alkaline earth metal silicates, natural silicates with free silicic acid groups and raij±ures thereof. The hydrated silica indu s various siliccn acids such as silicic acid gel, orthoεilicic acid, meta- silicic acid, monosilandiol, polysilicoforπic acid, etc. Hydrated silica is the preferred oxidated silicon compound.

Any suitable organic polyisocyanate may be used according to the invention, including aliphatic, cycloaliphatic, eraliphatic, aromatic and heterocyclic polyisocyanates. Suitable poiyisocya- nates are, for example, aryle e polyisocyanates such as tolylεne, r.etaphεnylene; 4-chlorophenylene-l,3-; ethylene-bis-(pr.enylsne-4-) ;

- TJRHXr

OMPI /., IPO

biphenylene-4,4 ^r -^ SjS-dimethox -bi henylene^^'—r 3,.3 ^r -di— phenylbiphenylene—4,4'—-^ naphthalene-l _r 5— and tetrahydronaphtha- lene—1,5-diisocyanates and triphenylmethane triisocyanate ; alky¬ lene polyisocyanates such as ethylene, ethylidene; propylene-1,2-; but.ylene-1,4-' butyl ne-1,3-; he:ylene-l,6-; decamethylene-1,10-**:- cyclohexylene-1,2-; cyclohexylene-l,4-J and methylene-bis—(cyclo- hexyl-4,4'-) diisocyanates.

It is generally preferred to use commerically readily avail¬ able polyisocyanate _r e.g., tolylene-2,4- and -2,6-dϋsocyanate and any mixtures of these iso ers, ("TDI") , polyphenyl-polymethy- leπe-isocyanates obtained by aniline-formaldehyde condensation followed by phosgenation ("crude MDI"), and polyisocyanates which contain carbodiimide groups, urethane groups, allophanate groups, isocyanu ate groups, urea groups, imice groups or biuret groups, ("modified polyisocyantes"). Inorganic polyiso¬ cyanates are also suitable according to the invention. Suitable polyisocyanates t-zhich may be used according to the invention are described, e.g., by W. Siefken in Justus Liebigs Annalen der Cheπάe, 562, pages 75 to 135.

Solutions of distillation residues accumulating during the production of tolylene diisocyanate, diphenyl methane diisocyanate cr riεxamethylene 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

OMPI

— *.- ^' -•-- ^' —11- " ' -

alkyl substituted on the nucleus, with aldehydes or ketones, may be used in this invention.

Organic polyhydroxyl compounds (polyols) 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 diiso- cyar.ates with from 1 to 50 mols of conventional organic com¬ pounds 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. While compounds which contain amino groups, thiol groups or carboxyl groups may bε used, it is preferred to use organic polyhydroxyl compounds, in particular, compounds which contain from 2 to S 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, polyethεrs, polythioethers, polyacetals, polycarbon¬ ates 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 homogeneous and cellular poiyurethar-es.

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 pclybasic, preferably dibasic, carboxylic acids _* Instead of

OMPI

the free pσlycarboxylic 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 pσlycarboxylic acid may be aliphatic, cycloali¬ phatic, aromatic and/or heterocyclic and may be substituted, e.g., with halogen atoms and nay be unsaturated.- Examples include: succinic acid, adipic acid, sebacic acid, suberic acid, azelaic acid,. hthalic acid, phthalic acid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride, -trimellitic acid, hexahydro- phthalic acid anhydride, tetrachlorophthalic acid anhydride, er.do- ethylene tetrahydrophthalic acid anhydride, glutaric acid anhy¬ dride, fumaric acid, maleic acid, maleic acid anhydride, dimeric and trimeric fatty acids such as oleic acid, optionally mixed ιτith monomeric fatty acids, dimethylterephthalate and bis-glycol tere- phthalatε. Any suitable polyhydric alcohol may be used such as, for example, εthylεne glycol; propylene-1,2- and -1,3-glycol; butylεne- ,4- and -2,3-glycol; hexane-l,6-dioi; octane-l,8-diσl; neopentyl glycol; cyclohεxanedimεthanol-(1, -biε-hydroxymethyl- cyclohexane) ; 2-methyl-propane- ,3-diol; glycεrol; trimethylol propane; hexane-l,2,S-triol; butane-l,2,4-triol trimethylol ethane; pentaεrythritolj uinitol; mannitol and sorbitol; methyl- glycoside; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycols; dipropylene glycol; polypropylene

OMPI ,, -.. wIPO ^e -* R y

--- glycols; dibutylene glycol and pσlybutylene glycols _* The poly¬ esters may also contain a proportion, of carboxyl end groups _* Polyesters of lactor.es, such as -caprolactone, or hydroxycarbox- ylic acids such as -hydroxycaproic acid, may also be used _*

The polyethers with at least 2, generally from 2 to 8 - and preferably 2 or 3, hydroxyl groups used according to the in¬ vention are known and may be prepared, e.g., by the polymeriza¬ tion 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 ^" , or by addition of thεsε εpoxides, optionally as mixtures or successively, to start¬ ing components v/hich 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 ethylenediaminε. Sucrose poly- ^■ ethers such as those described, e.g., in German Auslegeschriften os. 1,176,358 and 1,054,938, 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) . Poly¬ ethers modified with vinyl polymers such as those which may be ob¬ tained 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.

-$TJRE $-

OMPI

-. . - , .---: • »i -

B "pσlythioethers* are meant _r in particular, the con¬ densation products of thiodiglycol with itself and/or with other glycols _t dicarboxylic acids, formaldehyde, a inocarboxylic acids or aminα alcohols _* The products obtained are polythio-mixed ethers or polythioether ester amides, depending on the cocom- _ ponent.

The polyacetals used may be, for example, the compounds which may be obtained from glycols, e.g., diethylene glycol, triethylene glycol, 44*-dihydroxydiphenylmethylmethane, hexaned- iol, 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-l,4-diol; and/or hexane-l,6-diol or diethylene glycol; triethylene glycol or tεtraεthylene glycol, with diarylcarbonates, e.g., diphenylcarbonates or phosgene.

The polyester amides and polyamides include, e.g., the predominantly linear condensates obtained from poly/alent satu¬ rated and unsaturated carbcxylic acids or their anhydrides and polyvalent saturated and unsaturated a ino alcohols, diamines, polyamines and mixtures thereof...

Polyhydroxyl compounds which already contain urethane or urea groups, modified or u-αncdified natural polyols, e.g., castor

OMPI WIPO

oil, carbohydrates and starches, may also be used _* Additional products of alkylene oxides with phenol ormaldehyde resins or with urea-formaldehyde resins are also suitable for the purpose of the invention _*

Examples of these compounds v/hich are to be used according _ to the invention have been described, e.g., in High Polymers, Volume XVT, "Polyurethanes, Chemistry and Technology", published by Saunders-Frisch Intersciεnce Publishers, IJew York, London, Volume I, 1962, pages 32 to ^* 42 and pages 44 to 54 and Volume II, 1964, pages 5 to 5 arid 198 to 199; and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 45 to 71.

If the polyisocyanates or the prepolymer v/hich contains KCO groups have a viscosity above 2000 cP at 25 C, it may be advan¬ tageous 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 poly- urethane silicate prepolymers may also be xzseά in this invention. ahen an aqueous solution of alkali metal cellulose polymer is being used to react with, or as a curing agent for polyiso¬ cyanates, it is advantageous in certain cases to use catalysts such as tertiary amines, e.g., triethylamir.e, tributyla-ine,

N-methyl-morphoIine _r N-ethyl-morpholine, tetramethylthylenediamine, pentamethyldiethylenetriamine, triethanolamine, triisopropanolamine, organo-πtetallic compound, e _* g _* tin acetate, tin octαate, tin ethyl hexoate, dibutyl tin diacetate, dibutyl tin dilaurate and mixtures thereof.

Other examples of 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, Munich, 1966, e.g., on pages 96 and 102. Sila-amines are suitable catalysts, e.g _* , 2,2~4-trimethyl-2- silamorpholine or ,3-diethyl a inomethyl tetramethyl disiloxane _* Suitable catalysts are also tetraalkyl ammonium hydroxides, alkali phenolatεs, alkali metal hydroxidεs, alkali phenolates, alkali- alcoholates and hexahydrotriasines.

Suitable flame-resistant compounds may be used v/hich contain halogen or phosphorus, e.g., tributylphosphate; tris(2,3-dichloro- propyl)-phosphate; polyoxypropylenechloro ethylphosphonate; cresyldiphenylphosphate; tricrεsylphosphate; tris-(beta-chloro- ethyl)-phosphate; tris(2,3-dichloropropyl)-phosphate; triphenyl- phosphate; ammonium phosphate; perchlorinated diphenyl; perchlor- inated terephenyl? hexabromocyclodecane; tribrcmophenol; dibromo- propyldiene; hexabromobenzεne; octabromodiphenylether; pentabromo- toluol; poly-tribromostyrol; tris-(bromocresyl)-phosphate; tetra- bromobis-pher.ol AΪ tetrabromophthalic acid anhydride; octabromo-

diphenyl? tri-(dibromopropyl)-phosphate; calcium hydrogen phos¬ phate? sodium or potassium dihydrogen phosphate; disodiuitt or dipotassium- hydrogen phosphate; ammonium chloride; phosphoric acid; pσly/inylchlσride tetomers chloroparaffins as well as fur¬ ther phosphorus- and/or halogen-containing flame-resistant _ compounds as they are described, e.g., in "Kunststoff-Handbuch", Volume VH, Munich 1966, pages 110-111, which is incorporated herein- by ^' reference _* The organic halogen-containing components are, however, preferred in the polyurethane-cellulose and poly- urethane-cellulose-silicate cellular- solid products _* In the pro¬ duction of aldehyde cellulose, amino-aldehyde-cεllulose and phenol- aldehyde-cellulose cellular solid product, phosphoric acid may be used to react with the alkali-metal atoms, thereby producing ar. alkali metal hydrogen phosphate which may be used as the flame- resistant compound.

DETAILED DΞSC-RIFrlO!. OF THE ^~~~~ 2 ^~~~~~ O ^~~

The preferred process to produce the water-soluable alkali metal cellulose polymer 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 compound, then to heat the mixture at ambient pressure vAiile agitating at 150 C to 220 C for 5 to 60 minutes, thereby producing an alkali metal cellulose polyme . The alkali metal cellulose polymer softens or

-18-

melts into a thicJc liquid at 150 to 220 C and when it cools _r it forms a solid mass, dark brown in color _*

The alkali metal cellulose is soluable in water and organic solvents such as alcohols, epichlorohydrin, chlorohydrin and other organic solvents _* _

The alkali metal cellulose may be neutralized (pH 7) with an acid compound to produce a foamed cellulose product by the production of CO v/hen the acid reacts with the alkali metal atoms to form a salt _* The foamed cellulose product may be dried and utilized for thermal and sound insulation in construction of buildings, cars, boats and airplanes. The foamed cellulose may be washed and filtered to remove the salt.

In an additional preferred process, about 2 parts by weight of the alkali metal cellulose polymer produced by the process of the invention are mixed with 1 to 5 parts by weight of an alde¬ hyde, the- agitated at ambient temperature for 10 to 60 minutes, thereby producing an aldehyde-alkali metal cellulose copolymer. The aldehyde-alkali metal cellulose copolymer may be reacted with an acid compound until the pH is 6 to ~ ^~ , thereby producing cellu¬ lar solid aldehyde-cellulose copolymer. The salt is removed by washing and filtering.

In additional preferred process, about 2 parts by weight of the alkali metal cellulose polymer produced by the process of

OM IP

this invention are mixed v/ith 1 to 5 parts by weight of an amino compound and 0 _* 5 to 5 mols of an aldehyde for each mol of the amino compound, then agitated at a temperature between ambient temperature and 100 C for them 10 minutes to 12 hours, thereby producing an aminoplast-alkali metal cellulose resin; — then an acid compound is added until the pH is 5 to 7, while agitating until the resin begins to expand, thereby producing a cellular solid.aminoplast-cellulose product _*

In an additional preferred process, about 2 parts by v/eight of the alkali metal cellulose polymer produced by the process of this invention are mixed v/ith 1 to 5 parts by weight of a phenol compound and 1 to 5 mols of an aldehyde per raol of the phenol compound, then agitated at a temperature from ambient to 100 C for from 10 minutes to 12 hours, thereby pro¬ ducing a phenoplast-alkali metal cellulose resin; then. n acid compound is added until the pH is 5 to 7 while agitating for a few seconds until the mixture begins to expand, thereby producing a cellular solid phenoplast-cellulose product.

The processes to produce cellular solid aminoplast-cellu¬ lose and phenoplast-cellulose cellular solid products may be combined to produce cellular solid phenoplast-cellulose-aminoplast products.

£TfREΛ

OMPI /., WIPO

-zσ-

In an additional preferred, process,' 1 to 4 parts by weight of the alkali metal cellulose polymer produced by the process of this invention and 3 parts by weight of an isocyanate-terminated polyurethane prepolymer-are rapidlymixed, and in a few seconds to about 120 minutes, the mixture expands 3 to 12 times its ori- • ginal volume to produce a cellular solid polyurethane-cellulose product _* -

In an additional preferred process, one part by weight of aqueous solution containing 20%; to 60% of the alkali metal cellu¬ lose produced by the process of this invention is mixed vith 1 to 10 parts by weight of an organic polyisocyanate or polyiso- thiocyanate; then in a few seconds to 120 minutes, the reaction is complete, thereby producing a polyisocyanate-cellulose cellu¬ lar solid or solid product.

In an additional preferred process, about 10 parts by weight of an aqueous solution containing 20% to 60% by weight of the alkali metal cellulose polymer produced by the process of this invention are mixed 10 to 100 parts by weight of an iso¬ cyanate-terminated polyurethane prepolymer and 0.001 to 0.01 parts by weight of an amine catalyst; then in a few seconds to 120 minutes,, the reaction is complete, thereby producing a poly¬ isocyanate-cellulose cellular solid or solid product _*

Ih an additional preferred process 1 to 3 parts by weight of the alkali metal cellulose polymer as produced by the pro¬ cess, of this invention, 1 to 3 parts by v/eight of an oxidated silicon compound, 1 to 3 parts by weight of a polyol and 3 parts by v/eight of an organic polyisocyanate or polyisothiocyanate are- rapidly mixed; then in a few seconds to 120 minutes, the reac¬ tion is complete, thereby producing a polyurethane-cellulose- silicate cellular solid or solid product.

In an additional ^' preferred process, two parts.by weight of the alkali metal cellulose produced by the process of this in¬ vention are mixed with 1 to 4 parts by v/eight of an organic polyisocyanate, then agitated for 10 to 60 minutes at a tempεra- ture between 20 C to 70 C, thereby producing a polyisocyanate- alkali metal cellulose prepolymer; then 10% to 100% by v/eight of a curing agent, based on v/eight of the prepolymer, is added to the prepolymer while agitating at 20 C to SO C for 5 to 20 min¬ utes, thereby producing a cellular solid or solid polyisocyanate- cellulose product.

In an additional preferred process, 1 to 3 parts by v/eight of the alkali metal cellulose produced by the process of this invention, 1 to 3 parts by v/eight of a polyol and 1 to 3 parts by veight of an organic polyisocyanate are rapidly mixed at am¬ bient temperature and pressure and in a few se'conds to 5 minutes,

-22-

the mixture expands 3 to 12 times its original volume, thereby producing a cellular solid polyurethane-cellulose produc .-

When the alkali cellulose polymer produced by this inven¬ tion is reacted v/ith an acid compound, CO _? is given off, and a foamed cellulose product is produced. In cases where inadequate- C0_ is produced to form cellular solid cellulose products, a blow¬ ing agent may be used _* . The blowing agent may be added to the alkali cellulose polymer or to an aqueous solution of ^" the.-alkali cellulose polymer before the acid compound is added. The blowing agent may be also added with the acid compound. The chemical re¬ action between the acid compound and the alkali metal atoms v/ill usually produce enough heat to evaporate or expand the blowing agent.

Readily volatile blowing agents, e.g., dichlorodifluoromethane, trichlorofluoromethane, butane, isobutylene or vinyl chioridε, may be used to produce cellular solid products in this in ^d ention _• In addition, the liquid reaction mixtures can be expanded into a foam by the introduction of gases, optionally under pressure, such as air, methane, CF^, noble cases and H_0 , the resulting foam being introduced into the required mold and hardened therein. The resultant f aπr may optionally contain foam stabilizers such as surfactants, foam formers, e ulsifiers 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 v/ith the other components, the resulting mix¬ ture being allowed to harden. Instead of blowing agents it is also possible to use inorganic or organic, finely divided hollow bodies such as expanded hollow beads of glass, plastic, straw, ex¬ panded clay, and the like, for producing foam _*

The foams obtainable in this way can be used either in their dry or their moist form if desired after a compacting or temper¬ ing process, optionally carried out under pressure, as insulating materials, etc. They can also be used in the form of sandwich elεments, for example, with metal-covering layers, in house, vehicle and aircraft construction _*

It is also possible to introduce into the foaming reaction mixtures, providing they are still free-flowing, organic and/or inorganic foamable or already foamed particles, for example, ex¬ panded clay, expanded glass, wood, popcorn, cork, hollow beads of plastic, for example, vinyl chloride polymers, polyethylene, styrene polymers or foam particles thereof or even, for example, polysulphone, polyepσxide, polyurethane, urea ormaldehyde, phenol forr.aldehyde, polymide polymers, urea-silicate-formaldehyde poly¬ mers, phenol-silicate-formaldehyde, epoxy silicate polymers, poly¬ isocyanate silicate polymers, polyurethane silicate polymers or the reaction mixtures 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

- OREΛ

OMPI !*£Se-

clay _r glass or slate v/ith the reaction mixture, according to the invention, are especially preferred _*

It is also possible to introduce into the foaming reaction mixture _τ providing they are still free-flowing, at a pre-deter- mined temperature, a blowing agent v/hich is capable of evapora- _ tion or of gas formation at these temperatures, for example, a halogenated hydrocarbon. 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 vith 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 inven¬ tion 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 _*

Since the hardened foams obtained by the process according to the invention can show considerable porosity after drying, trey are suitable for use as drying agents because they can absorb water? however, they can also be charged v/ith active substances or used as catalyst supports or filters and absorbents.

OMP V ^W /I ⁱ P

On the other hand, the foams can be subsequently lacquered, metallized, coated, laminated, galvanized, subjected to vapor de¬ position, 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 moldings can be further modified in their properties, by thermal after-treatment, oxidation processes, hot- -preεsing, sintering processes or surface melting or other consoli¬ dation 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, v/ood,- plastics such as PVC, polyethylene, epoxide resins, ABS, polycarbonate, etc.

Fillers in the form of particulate or powdered materials can bε 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, Al—, Fe-, Cu-, Ag-pov/der, molybdenum sulphite _r steel wool,- bronze or copper cloth, silicon pov/der, expanded clay particles, hollow glass beads, glass pov/der, lava and pumicevparticles, wood chips, sawdust, cork, cotton, straw, jute, sisal, hemp, flax, rayon, _ popcorn, coke, particles of filled or unfilled, foamed or un¬ foamed, stretched or unstretched, organic polymers including plastics and rubber waste _* Of the number of 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, poly- acetal resins, polyepoxides, polyhydantoins, polyurea, poly¬ ethers, polyurethanes, polyimides, polysulphones, polycarbonates, and, of course, any copolymers as well. Inorganic fillers are ^■ preferred.

Generally, the composite materials according to the inven¬ tion can be filled vith considerable quantities of fillers with¬ out losing their valuable property spectrum. The amount of fillers can exceed the amount of the reactants. In special cases, the foamed products of the present invention act as a binder for such fillers.

Basically, 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-opera¬ ting 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 re¬ quired for this, v/hich may be from 0 C to 200 C and preferably from 20 C to 160 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 re¬ action 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 temp¬ erature to rise to values above 50 C after the reaction or foaming has begun.

In particular, hov/ever, the process according to the inven¬ tion 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 v/ay _*

The alkali cellulose polymers as produced in this invention may be pre-reacted with an aldehyde, then foamed by the addition of an acid compound. The foamed particles may be dried and used

OMPI

as insulation material by pouring a layer of the particles be¬ tween rafters and studs in. houses-, buildings, etc..

The alkali cellulose polymers as produced in this invention may be pre-reacted v/ith an amino compound and an aldehyde to pro¬ duce a liquid alkali cellulose-amino-aldehyde, then placed in a — mixing chamber, optionally adding a blowing agent, emulsifier, 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 sav/ed 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 pov/der and molded into use¬ ful products by heat and pressure in a mold.

The alkali cellulose polyme -as produced in this invention may be pre— eacted v/ith a phenol compound and an aldehyde to pro¬ duce a liquid polymer, his liquid polymer may be foamed in the sane manner as the a ino-aldehyde-cellulose polymers and may be

OM WIP

used for the same purposes, sound and thermal insulation, molding povder and in the production of paints, varnishes,, adhesives,. etc _* The liquid phenoplast 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— eacted v/ith a phenol compound, an amino and an aldehyde compound to produce a liquid resin _* This liquid resin may be poured into a mold, then heated to 70 C to 100 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, option¬ ally 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-cellulose-aminoplast resins may be used as molding powder and molded by heat and pres¬ sure into useful objects. The phenσplast-cellulose-a-mir.oplast re¬ sin may be foamed into large slabs, then sawed into various sizes

and thicknesses or broken into small particles and used for ther¬ mal and sound insulation in houses, buildings, vehicles and air- crafts; 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 insu¬ lation 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 poly¬ isocyanate cellulose foam, polyurethane cellulose foam and poly- urethane-silicate-cellulose foam is particularly suitable, hov/ever, for in situ foaming on the building site. Any hollow molds nor¬ mally 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-retar- dant agent, diluents, deodorants, coloring agents and other agents, produced by adding the components simultaneously to a mixing appa¬ ratus, 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., v/here it may be left to harden. The foaming reaction mixture may also be forced, cast or in ection molded into cold or heated molds, then hardened, optionally under pressure and at room temperature or at temperatures up to 200 C, optionally using a centrifugal casting process _* At this stage,

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-iπpregna- tion process or by processes in v/hich 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 addi¬ tion of the oxidated silicon compounds. On the other hand, 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 carriers of other active substances, as decoration elements, shock-resistant packaging, furniture components and cavity fill¬ ings. 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.

OMPI /., WIPO _v \.

The mold may be in the forπr 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 in the form of droplets or may be dispersed, e.g., in petroleum hydrocarbons or v/hile they are under condition of free fall. — Foam beads are obtained in this way. The foamed products pro¬ duced by these methods may also be added in a crumbly form to soil,- optionally v/ith the addition of fertilizers and plant-pro¬ tective agents so as to improve the agricultural consistency of the soil. Foams v/hich have a high 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 foaπung mixtures may also ^" be used underground in caves, mines, tunnels, etc., by spraying the foaming mixtures onto wire mesh, fiberglass cloth, woven fabrics or*directly on the walls, to produce pro¬ tective layers to prevent accidents.

It is also possible to introduce into the foaming reaction mixtures, providing they are still free- lowing, organic and/or organic foamable or already foamed particles such as expanded clay, expanded glass, v/ood,, popcorn, cork, hollov/ 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, or to allow thε reaction mixtures to foam through interstitial space in packed volumεs of these particles,- and in this v/ay to produce insulating materials v/hich are distin¬ guished by excellent flame behavior. Combinations of expandεd clay, glass, or slate with the reaction mixtures, according to the invention, are especially preferred. DESCRIPTION OF PREFERRED EMBODIMENTS

My invention v/ill be illustrated in greater detail by the specific examplεs which follow, it being understood that these preferred embodiments are illustrative of, but not limited to, procedures v/hich may be used in the production of alkali metal cellulose polymers. Parts and percentages are by weight unless otherwise indicated.

Exanrole 1

About 1 part by v/eight of lye flakes (NaOH) and 2 parts by v/eight of fir sawdust are mixed, then heated to 150 C to '220 C while agitating at ambient pressure, v/ith -care being taken for the mixture .not to burn, for 5 to SO minutes or until the mixture softens and expands into a dark-brown, thick liquid when hot. It cools to a solid, thereby producing an alkali etal cellulose poly¬ mer, sodium cellulose.

About three-fourths of the original sawdust is soluable in v/ater, and the other fourth is soluable in organic solvents such as alcohols.

Examole 2

About equal parts by v/eight of dry pine sawdust and sodium _ hydroxide falkes, 20 gm. each, are mixed in a beaker, then heated to about 150 C while agitating for about 5 minutes; the mixture begins to expand, and is rεmovεd from the external source of heat. The mixture continues to soften and expand as the temper¬ ature rises to about 180 to 220 C, thereby producing a dark- brown, thick liquid while hot which then cools to a solid product. About 90% of the original sawdust is soluable in v/ater.

Example 3

About 2 parts by v/eight of potassium hydroxide and 3 parts by v/eight of white oak sawdust are ^' .xed, then heated to 150 to 220 C while agitating at ambient pressure for 5 to 60 minutes or until all the sawdust softens and expands into a thick liquid, thereby producing potassium cellulose polymer.

Example 4

About 2 parts by weight of sodium hydroxide and 3 parts by weight of dry small particles of the various woods listed below o o arε mixed, then heated to 150 C to 220 C while agitating at am¬ bient pressure for 5 to 60 minutes, thereby producing sodium cell¬ ulose polymer.

The v/ood is selected from the group consisting of fir, pine, rεdv/ood, cedar, oak, spruce, gum, hemlock, walnut, hickory, eucalyp¬ tus, birch,* poplar, beech, maple, mahogany, aspen, ash, cypress, elm, cherry, sycamore, and mixtures thereof.

Example 5 —

About 2 parts by v/eight of sodium hydroxide flakes and 3 parts by weight of cellulose in the form of cotton are mixed, then heated to 150 C to 220 C while ^" agitating at ambient pressure for 5 to 60 minutes, thereby producing sodium cellulose polymer.

Other cellulose products may be used in place of cotton, such as wood pulp with lignin removed by soda process, v/ood pulp v/ith lignin removed by the acid sul ite process, v/ood pulp f om waste paper and mixtures thereof.

Example 5

About 2 parts by weight of sodium hydroxide flakes and 3 parts by v/eight of small particles of dried seaweed are mixed, then heated while agitating to 150 C to 220 C for 5 to 60 r-inutes, thereby producing a water-soluable mixture of sodium alcinate and sodium cellulose v/ith alginic acid still attached to the cellulose.

Example 7

About 2 parts by veight of sodium hydroxide flakes and 4 parts by v/eight of dry small particles of seaweed v/ith the alginic acid extracted v/ith a sodiurs carbonate solution are mixed, then

OMPI SATIOI

heated to 150 C to 220 C while agitating for 5 to 60 minutes, thereby producing sodium cellulose polymer.

Example 8

About 2 parts by v/eight of sodium hydroxide flakes, 2 parts by v/eight of dried seaweed and 1 part by v/eight of fir sawdust — are mixed, then heated to 150 C to 220 C while agitating for 5 to 60 minutes, thereby producing sodium cellulose and sodium alginate polymers.

Example 9

About 3 parts by weight of dry corn cobs ground into small particles about the size of sawdust and 2 parts by v/eight of sodium hydroxide flakes are mixed, then heated to 150 C to 220 C while agitating for 5 to 50 minutes, thereby producing a water-soluable, dark-brown sodium cellulose polymer.

Other agricultural cellulose-containing plants nay be used in place of com cobs, such as corn stalks, cotton stalks, rice straw, wheat straw, oat straw, barley straw, soybean stalks, cane sugar stalks (bagasse), pea vines, bean vines, sugar beet x/aste, sorghum stalks, tobacco stalks, maize stalks, buckwheat straw and mixtures thereof.

Example 10

About 2 parts by v/eight of sodium hydroxide, 1 part by v/eight of sawdust frcrr. spruce v/ood, 1 part by v/eight of chopped dry sea-

v/eed and 1 part by weight of ground cotton stalks are mixed, then heated to 150 C to 220 C v/hile agitating for 5 to 60 minutes, ^' thereby producing sodium cellulose containing a. small amount of sodium lignin and sodium alginate.

Example 11 _

About 2 parts by v/eight of sodium hydroxide flakes and 3 parts by v/eight of dried ground garden plants, containing about equal parts by. /eight of tomato plants, bean plants, pea vines, potato plants, grass and weeds, are mixed, then heated to 150 C to 220 C v/hile agitating for 5 to 60 minutes, thereby producing sodium cellulose polymer.

Example 12 About 1 part by v/eight of sodium hydroxide flakes and 3 parts by v/eight of dried algae are mixed, then heated to 150 C to 220 C v/hile agitating for 5 to 60 minutes, thereby producing sodium her-icellulosε polymer.

Example 13 About 2 parts by v/eight of sodium hydroxide flakes, 1 part by v/eight of pine v/ood sawdust, 1 part by weight of dry algae and 1 par- by weight of dry particles of Johnson grass are mixed, then heated to 150° C to 220° C v/hile agitating for 5 to 50 min- -es, thereby producing sodium cellulose polymer.

OMPI WIPO

Examplε 14 About 4 parts by v/eight of the sodium cellulose polymer as produced in Example 1 are added to 6 parts by weight of v/ater, then filtered. About 0.5 part by v/eight of the sodium cellulose polymer is not soluble---in v/ater. Hydrochloric acid is added to - the aqueous solution of. sodium cellulose until the pH is about 7, carbon dioxide is given off and cellulose polymer precipitates out. The aqueous solution is filtered off, therεby recovering the cellulose polymer. The aqueous solution is evaporated and contains about 0.5 parts by v/eight of lignin and cellulose.

Examp -le 15

About 4 parts by v/eight of the sodium cellulose polymer as produced in Example 1 is mixed with 2 parts by v/eight of water to form a thick paste; then an aqueous solution containing about 50% sodium hydrogen sulfate is added to the sodium cellulose poly¬ mer in the amount to produce a pH of about 6 to 7 and is rapidly mixed. The mixture expands 3 to 4 times its original volume to produce a cellular solid cellulose polymer. The ^" sodium sulfate is removed by washing and filtering.

Example 16 .

About 4 parts by v/eight of the sodium cellulose polymer as produced in Example 2 are mixed with 8 parts by v/eight of v/ater. The sodium cellulose aqueous solution is filtered, and about 0.2 part by v/eight of the sodium cellulose polymer ^" is not soluable.

OMPI WIPO

Dilute sulfuric acid is added to the aqueous solution until the pH is 6 to 7; carbon dioxide evolves, and the cellulose polymer is precipitated. The aqueous solution is filtered, thereby re¬ covering the cellulose polymer. The aqueous solution is evapo- ratεd and about 0.5 part by v/eight of cellulose and lignin is re¬ covered.

Example 17

4 parts by weight of the sodium cellulose polymer as pro¬ duced in Example 1 are mixed with 6 parts by weight of an aqueous solution containing 37% formaldehyde, then heated to 70 C to 100 C v/hile agitating for 30 to 120 minutes, thereby producing a formaldεhydε sodium cellulose copolymer.

Example 18

About 4 parts by v/eight of the formaldehyde sodium cellulose copolymer as produced in Example 15 are mixed v/ith phosphoric acid until the pH is about 6 tc 7; the mixture expands 3 to 5 ti-^es its original volume, thereby producing an aldehyde-cellulose cellu¬ lar solid product.

Example 19

About 3 parts by v/eight of the potassium cellulose polymer as produced in Example 3 and 2 parts by v/eight of furfural are mixed, then agitated at ambient temperature for 10 to 120 minutes, thereby producing an aldehyde-potassium cellulose ccpolyrαer.

Othεr aldehydes may be used in place of furfural such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, acrolein, butyl aldehyde, pentanals, hexanals, heptanals, octa-*- nals, and mixtures thereof.

Example 20

To about 3 parts by weight of each of the aldehydε-potas- siu cellulose copolymers produced in Example 19 is added an acid compound, hydrochloric acid, until the pH is 5 to 7. The mixture expands 3 to ^" 6 times its original volume, thereby pro¬ ducing a cellular solid aldehyde-cellulose product.

Other acid compounds may be used in place of hydrochloric acid such as mineral acids, organic acids, inorganic hydrogen- containing salts and mixtures ^' thereof.

Example 21

2 parts by weight of sodium cellulose polymer as produced in Example 1, 1 part by '.-/eight of urea and 3 mols of an aqueous solution containing 37% formaldehyde for each mol of urea are mixed, then agitated at a temperature between ambient tempera¬ ture and 100 C for 10 minutes to 12 hours, thereby producing. an a inoDlast-alkali metal cellulose resin.

OMP WIP

Example 22 To about 2 parts by v/eight of the aminoplast-alkali metal cellulose resin produced in Example 21 are added about equal parts by v/eight of concentrated hydrochloric and phosphoric acid until the pH is 5 to 7. The components are rapidly mixed, the mixture_ expanding 3 to 10 times its original volume, thereby producing a rigid cellular solid aminoplast-cεllulose product.

Example 23 2 parts by v/eight of the -sodium cellulose polymer as produced in Example 1, 1 part by v/eight of the sodium cellulose polymer containing the sodium alginate as produced in Example 6, 2 parts by v/eight of an amino compound, selected from the list be¬ low, and 5 mols of an aldehyde for each mol of the amino com¬ pound, selected from the list below, are mixed, then agitated at a temperature between ambient temperature and 100 C for 10 min¬ utes to 12 hours, thereby producing an aminoplast-alkali metal cellulose resin.

Example Amino Compound Aldehyde a urea acetaldehyde b thiourea propionaldehyde c melaminε . crotonaldehyde d 1,3-dibutylthiourea furfural a ,3-dibutylurea acrolein f ethylenediamine butyl aldehyde propylenediamine bεnzaldehyde

9 h diethylenetriamine formaldehyde i 1,3-dipropylurea paraformaldehyde aniline formaldehyde

Example 24

To about 2 parts by weight of each of the aminoplast-alkali metal cellulose resins produced in Examplε 23 is added an acid com¬ pound, hydrochloric acid, until the pH is 6 to 7, while rapidly mixing. The mixture expands 3 to 10 times its original volume, thereby producing cream-colored, rigid, cellular solid aminoplast- cellulose products.

Other acid compounds may be used in place of hydrochloric acid such as other mineral acids, organic acids, salt-producing organic compounds, inorganic hydroge -containing salts and mixtures thereof.

OMPI

Examplε 25 About 2 parts by v/eight of an alkali metal cellulose polymer, listed belov/, 1 part by v/eight of a phenol compound, listed be¬ low, and 3 mols of an aqueous solution of formaldehyde for each mol of the phenol compound are mixed, then agitated at a tempera¬ ture between ambient and 100 C for 10 minutes to 12 hours, thereby producing a phenoplast-alkali metal cellulose resin.

Example Alkali metal cellulose polymer Phenol compound a of Example 1 phenol b of Example 2 cresol c of Example 3 creosote d of Example 4 p-cresol c

! of Example 5 o-cresol

! j of Example 6 m-cresol g of Example 7 cresylic acid h of Example 8 resorcinol of Example 9 cashew nut shell liquid

J of Example 10 Bisphenol A k of Example 11 2,6-dimεthylphenol

1 of Example 12 p'tert-butyl phenol

^{' *} : ^' - ^* -44-

Example 26

To each of the phenoplast-alkali metal cellulose resins pro¬ duced in Example 25 is added an acid compound phosphoric acid, until the pH is 6 to 7 while rapidly mixing. The mixture expands 3 to 10 times its original volume, thereby producing a cellular - solid phenoplast-cellulose product.

Example 27

Example 25 is modified, wherein 1 part by v/eight of urea is added to the phenol compound, thereby producing an aminoplast- phεnoplast-alkali mεtal cεllulosε resin; then ^" in Example 26 a light-brov.n-colored, cellular solid aminoplast-phenoplast-cεllu- lose product is produced.

Example 28

About 2 parts by v/eight of the sodium cellulose polymer, as produced in Example 1, 2 parts by weight of urea, 0.5 part by v/eight of crεsylic acid and 3 mols of an aqueous solution of for¬ maldehyde for each mol of urea and cres lic acid are mixed at 50 C; then 0.5 part by v/eight of chloroform and sufficient hydro¬ chloric acid are added to produce a pH of 6 to 7 v/hile rapidly mixing. The mixture expands 3 to 10 times its original volume, thereby producing a light-brown, rigid, tough, cellular solid ainoplaεt-phenoplast cellulose product.

OMP

Exaπple 29

About 2 parts by weight of an alkali metal cellulose, as produced in Example 1, and -1 part by v/eight of tolylene diiso¬ cyanate are mixed, then agitated for 10 to 60 minutes at a temp¬ erature between 20 C to 70 C, thereby producing a polyisocyanate- alkali metal cellulose prepolymer. Then 0.4 part by weight of v/ater containing 5% triethyla ine is added to the prepolymer v/hile agitating for 5 to 20 minutes or until the mixture begins to expand. It expands 3 to 10 times its original volume, thereby producing a light-brown-colored, tough, cellular solid polyiso- cyanate-cellulose product.

Other alkali metal cellulose polymers may be used in place of that produced in Example 1, such as those produced in Examples 2,3,4,5,6,7,8,9,10,11,12 and mixtures thereof.

Other curing agents may be used in place of the v/ater con¬ taining 5% by weight of triethylamine such as v/ater, v/ater con¬ taining 1% to 10% by weight of other amine catalysts, v/ater con¬ taining 10% to 60% by v/eight of a polyhydroxy compound, water con¬ taining 10% to 60% by v/eight of silica sol, v/ater containing up to 5% by v/eight of an emulsifying agent, v/ater containing 10% to 50% bv eiσht of sodium silicate and mixtures thereof.

-45-

Example 30 About 2 parts by v/eight of a powdered alkali metal cellulose polymer, as listed belov/, 2 parts by v/eight of a polyol, listed belov/, and 2 parts.by v/eight of tclylene diisocyanate (80% 2,4- isomεr and 20% 2,6-isomer) are added simultaneously, then rapidly mixed. In a few seconds to 10 minutes, the mixture expands about 8 to 12 times it original volume to produce a rigid, tough, cellular solid polyurεthane cellulose product.

Example | Alkali metal cellulose polymer Polyol a j as produced in Example 1 •- clvcerol b j as produced in Example 2 [ triethylenε glycol i c ; as produced in Example 2 ; propylεnε glycol - i d ; as produced in Example 4 f butylene glycol e i as produced in Example 5 polyethylene glycol (mol ^' . wt. 4c0) f as produced in Example 5 polypropylene glycol (mol. wt. 500) i g as produced in Example ~ polyethylene glycol

as produced in Example 8

as produced in Example

5 mol phthalic acid)

Example 31

About 2 parts by v/eight of the powdered potassium cellulose polymer as produced in Example 3, and 2 parts by v/eight of the powdered sodium cellulose polymer and sodium alginatε, as pro¬ duced in Example 6, and 5 parts by weight of an isocyanate-ter¬ minated polyurethane prepolymer, listed belov.-, are thoroughly

mixed; then in a fev/ seconds to about 10 minutes, the mixture be¬ gins to expand, expanding 3 to 12 times its original volume to •produce a tough, rigid, cellular solid, poyurethane product.

Example Isocyanate-terminated polyαrethane prepolymer toluene diisocyanate v/ith polypropylene glycol (mol. wt. 520) in an CO/OH ratio of 25:1.

20% solution of a distillation residue of the distil¬ lation of commercial tolylenε diisocyanate in a crude phoεphosge ation product of an aniline- formaldehyde concensation with an NCO content of about 30%, with polyethylene glycol (mol. wt. 1000) to produce an isccyanate-terminal polyurethane pre¬ polymer v/ith an I.CO content of about 17%. diisocyanatodiphenyimethane with a tetrafunctional polypropylene glycol (mol. wt. 500) to produce a prepolyrer having about 22% NCO groups. toluene diisocyanate with a liquid hydroxyl-termin¬ ated polybutadier.e (mol. wt. about 1000) available from Arco Chemical- Co. under the trade designation of "POLY B-D R-15I-." and "POLY B-D R45M" to produce a orepoivmεr v/ith an NCO content of about 7%.

OM

ΛVΠ-

Examole Isocyanate-terminated polyurethane prepolyir-e-- toluene diisocyanate v/ith castor oil to produce a prepolymεr v/ith an NCO contεnt of about 15%. toluene diisocyanate v/ith a hydroxyl-group-con- taining polysulfide polymer to produce a prepoly¬ mer v/ith an NCO content of about 12%. raethylene bis-phenyl diisocyanate v/ith a liquid polyepichlorohydrin to produce a prepolymer of about 16% and 25% by weight of a resin extender, polyalpha-πethyl-styrene, is added, percentage based on v/eight of prepolyner. polyphenyl-pclymethylene-isccyanate v/ith polyethylene oxide monohydric alcohol (r.ol. wt. 1145), initiated on trimethylol propane to produce a prepolymer v/ith an NCO ^' contεnt of about 1S%. residue of tolylene diisocyar.ate distillation, v/ith about 20% by weight of NCO with polyethylene glycol (mol. wt. 1500) to produce a prepolymer v/ith an NCO content of about 11%. tolylene diisocyanate with a polyester (4 cls of glycerol, 2.5 mols of adipic acid and 0.5 r.ol of phthalic anhydride) to produce a prepolymer v/ith an NCO content of about 23%.

xample Isocyanate-term nated polyurethane prepolymer tolylene diisocyanate v/ith polyethylene (mol. wt. 2000) to produce a prepolymer with an NCO con¬ tent of about 28%. _

Example 32

About 2 parts by weight of sodium cellulose polymer as pro¬ duced in Example 2 is mixed v/ith 2 parts by v/eight of water to produce a thick aqueous solution v/hich is then mixed thoroughly v/ith 0.01 part by v/eight of triethylεneamine and 3 parts by v/eight of tolylene diisocyanate. The mixture begins to expand in 1 to 20 minutes. It εxpands 3 to 10 times its original vol¬ ume, thereby producing a rigid, cellular solid, polyisocyanate- silicate product.

Example 33

About 4 parts by v/eight of sodium cellulose polymer as pro¬ duced in Example 1 are mixed v/ith 5 parts by v/eight of v/ater, 0.02 part by v/eight of triethanolamine, 0.05 part by weight of sodium dioctyl εulfosuccinate and 0.1 part by wεight of trichloro- fluoromethane, then thoroughly mixed v/ith an organic polyisocyanate, listed below. The mixture expands 3 to 10 times its original vol¬ ume, thereby producing a rigid, cellular solid polyisocyanate- εilicate product.

The polyisocyanates used in this Examplε are: tolylene- 2,4- and -2,6-diisocyanate and mixtures thereof, polyphenyl-poly- methylene-isocyanate, diisocyanatodiphenylmethane, methylene bis phenyl diisocyanate, residue of tolylene diisocyanate v/ith about 20% by weight ^' of NCO, metaphenylene, sulphonated polyphenyl-poly- methylεne-polyisocyanate (sulphur content: about 1% isocyanate content: 30%) and 20% solution of a distillation residue of the distillation of commercial tolylene diisocyanate in diisocyanato- diphεnylmεthanε.

Examp -le 34

Example 31 is modified, wherein vater is added to the alkali metal cellulose polymer to produce an aqueous solution containing 50% by weight of alkali metal cellulose, thereby producing poly¬ urethane cellulose cellular solid products.

Example 35

An aqueous solution containing 60% sodi-rr. cellulose polymer, as produced in Example 1, and 1% by weight of triethyl mine are mixed v/ith an isocyanate-terminated polyurethane prepolymer, which was produced by reacting tclylene diisocyanate v/ith poly¬ ethylene (mol. wt. 1000), in the ratio of 3 parts by v/eight of the aqueous solution to Ξ parts by v/eight of the prepolymer. The mixture expands to 3 to 10 times the original volume, thereby producing a tough, rigid, ^' cellular solid pclyrethane-cellulose product.

Example 35 ^'

About 2 parts by v/eight of an alkali metal cellulose poly¬ mer as produced in Example 1, 2 parts by weight of a fine, gran¬ ular oxidated silicon compound, hydrated silica, 1 part by veight of a polyol, polyethylene glycol (mol. v/t. 1000) and 3 parts by- v/eight of a polyisocyanate, tolylene diisocyanate, are simul¬ taneously mixed in a rapid-speed mixer and then poured into a mold. The mixture expands 3 to 10 times its original volume, thereby producing a tough, light-brovn-colored, cellular solid polyurethane silicate product.

Other oxidated silicon compounds may be used in place of hydrated silica such as silica, e.g., silicoformic acid, poly- silicoformic acid, silicic acid gel, silica sol, etc.; alkali metal silicates, e.g., sodium silicate, potassium silicate, lithium silicate, etc.; alkaline earth metal silicates, e.g., calcium silicate, natural silicates v/ith free silicic acid groups, ammon¬ ium silicate; and ixthrεs thereof.

E ple 37

About 2 parts by weight of fine granular potassium cellulose polymer, as produced in Example 1, 3 parts by v/eight of silica sol, 2 parts by v/eight of a polyester (containing 16 mols of adipic acid, 16 mols of diethylene glycol and 1 mol of trimethylol pro¬ pane), 2 parts by v/eight of tolylene diisocyanate and 1 part by weight of polyphenyl-polymethylenε-isocyanate are thoroughly and

OMPI

-- ^{■ :} - - . ^" - - ^{'•' ' "} . ^{" "} -53- ^"""

rapidly mixed at ambient temperature. The mixture begins to ex¬ pand in a fev/ seconds to 10 minutes and expands 3 to 10 times its original volume, thereby producing a tough, light-brov/n-colored, cellular solid polyurethane silicate product.

Example 38 _

About 2 parts by v/eight of the powdered, sodium cellular poly¬ mer, as produced in Example 5, 1 part by v/eight of sodium silicate, 2 parts by v/eight of polypropylene glycol (mol. vt. 500) and 3 parts by v/eight of poϊyphenyl-polymεthylεne-isocyanate arε thoroughly and rapidly mixed at ambient temperature ana pressure. The mixture begins to expand in a fev/ seconds to 10 minutes and expands 3 to 10 times its original volume, thereby producing a tough, cellular solid polyurethane silicate product.

Although specific materials and conditions were set forth in the above examples, these were merely illustrative of pre¬ ferred embodiments of my invention. Various other compositions, such as the typical materials listed above, may be used where suitable. The reactive mixtures and products of my invention may have other agents added thereto in order to enhance or other¬ wise modify the reaction and products. Other modifications of my invention v/ill occur to those skilled in the art upon reading my disclosure. These are intended to be included within the scope of my invention, as defined in the appended claims.