Process for the production of polyisocyanate silicate plastics utilizing an alkali metal cellulose silicate condensation product

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BACKGROUND OF THE INVENTION

This invention relates to a process for the production of polyisocyanate silicate plaster utilizing a cellulose silicate condensation product, an organic compound having at least two isocyanate groups, an organic amphiphilous compound and a curing agent and/or activator.

The products produced by this invention have many commercial uses and may be utilized as thermal-insulating material, noise-insulating material, floatation materials in boats, shock-resistant packaging, cushions, as fiber, as coating agents, as fillers, as impregnating agents, as adhesives, as casting material, as putty materials, as as caulking materials, as constructional components of a building, etc. The products are novel, economical, possess improved heat- and flame-resistant properties and some have wood-like physical properties. The products may be produced by spraying or mixing in place.

In the process according to the invention, at least 3 components are used to produce the novel polyisocyanate silicate plastics as follows:

1. Component A: an alkali metal cellulose silicate condensation product;

2. Component B: an organic polyisocyanate or polyisothiocyanate;

3. Component C: an amphiphilous organic compound;

4. Component D: optionally, a curing agent and/or activator.

Component A

Component A, an alkali metal cellulose silicate condensation product, is produced by the processes outlined in my copending U.S. Patent Application Ser. No. 029,202, filed Apr. 12, 1979, and is incorporated into this invention.

Alkali metal cellulose silicate polymers are produced by mixing 3 parts by weight of a cellulose-containing plant or plant derivative with 1 to 2 parts by weight of an oxidated silicon compound and 2 to 5 parts by weight of an alkali metal hydroxide, then heating the mixture at 150.degree. C. to 220.degree. C. while agitating for 5 to 60 minutes.

Any suitable plant or the products of plants which contain cellulose may be used in this invention. The plant material is preferred to be in the form of small dry particles such as sawdust. Suitable plants include, but are not limited to, trees, bushes, agricultural plants, weeds, straw, vines, flowers, kelp, algae and mixtures thereof. Wood is the preferred plant. Commercial and agricultural waste products may be used, such as stalks, paper, cotton cloths, bagasse, etc. Wood fibers (wood pulp) with the lignin removed may be used in this invention. Plants that have been partially decomposed, such as humus, peat, certain soft brown coal, manure containing cellulose, etc., may also be used in this invention.

Any suitable oxidated silicon compound may be used in this invention. Suitable oxidated silicon compounds include silica, e.g., hydrated silica, hydrated silica containing Si-H bonds (silicoformic acid), silica sol, silicic acid, silica, etc.; alkali metal silicates, e.g., sodium silicate, potassium silicate, lithium silicate, etc., natural silicates with free silicic acid groups and mixtures thereof. Silica is the preferred oxidated silicon compound.

Any suitable alkali metal hydroxide may be used in this invention. Suitable alkali metal hydroxides include sodium hydroxide, potassium hydroxide and mixtures thereof. Sodium hydroxide is the preferred alkali metal hydroxide.

The process for the production of alkali metal-cellulose-silicate condensation product may be found in my copending U.S. Patent Application, Ser. No. 029,202, filed Apr. 12, 1979, and is incorporated in this Application.

The broken down alkali metal plant silicate condensation products are produced by mixing about 3 parts by weight of a cellulose-containing plant in the form of small particles with 1 to 2 parts by weight of a fine, granular oxidated silicon compound and 2 to 5 parts by weight of an alkali metal hydroxide. The mixture is then heated to 150.degree. C. to 220.degree. C. while agitating for 5 to 60 minutes, thereby producing a water-soluble alkali metal cellulose silicate condensation product. The condensation product is ground into small particles or powder. Care must be taken to avoid having the mixture catch on fire. Sodium hydroxide is the preferred alkali metal silicate and hydrated silica is the preferred oxidated silicon compound. Wood is the preferred plant.

Any unreacted wood or oxidated silicon compound may be used as a filler.

Component B

The polyisocyanate organic silicate solid/cellular solid products may be modified or improved by adding organic compounds, inorganic compounds, and/or organic-silicate compounds and polymers. These compounds may be added before the isocyanate and the oxidated silicon compounds are reacted together, or they may be added after the polyisocyanate silicate prepolymer is produced. Organic polyols, polyesters, polyether glycols, organic polyol silicates, polyester silicates and polysulfides, polybutadiene, butadiene-styrene copolymers and butadiene-acrylonitrile copolymers which contain free hydroxyl groups may be used in this invention. These hydroxyl-containing compounds (polyols), polymers and copolymers may be first reacted with a polyisocyanate to produce a liquid isocyanate-terminated polyurethane prepolymer, and this may be used in this invention. The polyols may be reacted chemically with oxidated silicon compounds to produce organic hydroxyl silicate compounds and their condensation products and may be used in this process. The method to produce the organic hydroxy silicate compounds and condensation products (polyester silicate polymers) may be found in U.S. Patent Application Ser. No. 765,050, filed on Feb. 2, 1977 by David H. Blount, M.D. The oxidated silicon compounds may be first reacted with a polycarboxylic acid and/or a polycarboxylic acid anhydride to produce a silicic acid organic acid anhydride which may then be reacted with a polyol to produce a polyester silicate polymer which may be used in this invention.

Any suitable polyisocyanate or polyisothiocyanate may be used in this invention: for example, arylene polyisocyanates such as tolylene; metaphenylene; 4-chlorophenylene-1,3; methylene-bis (phenylene-4); biphenylene-4,4'; 3,3'-dimethoxybiphenylene-4,4'; 3,3-diphenylbiphenylene-4,4'; napthalene-1,5; and tetrahydronaphthalene-1,5-diisocyanate and triphenylmethane triisocyanate; alkylene polyisocyanates such as ethylene; ethylidine; propylene-1,2; butylene-1,4; butylene-1,3; hexylene-1,6; decamethylene-1,10; cyclohexylene-1,2; cyclohexylene-1,4; and methylene-bis (cyclohexyl-4,4) diisocyanates. Phosgenation products of aniline-formaldehyde condensation may be used, such as polyphenyl-polymethylene polyisocyanates. Polyisothiocyanates, inorganic polyisothiocyanates, polyisocyanates which contain carbodimide groups as described in German Pat. No. 1,092,007 and polyisocyanates which contain urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups may be used to produce polyisocyanate silicate prepolymers or polyisocyanate organic silicate solid/cellular solid products. Mixtures of the above-mentioned polyisocyanates may be used.

It is generally preferred to use commercial, readily available polyisocyanates such as toluene-2,4 and -2,6-diisocyanate and any mixture of these isomers, ("TDI"), ("crude MDI"), polyphenyl-polymethylene-isocyanates obtained by aniline-formaldehyde condensation followed by phosgenation, and modified polyisocyanates which contain carbondiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups ("modified polyisocyanates") and mixtures thereof.

Other polyisocyanates may be used in this invention, such as polyisocyanates which contain ester groups such as those listed in British Pat. Nos. 956,474 and 1,086,404; in U.S. Pat. Nos. 3,281,378 and 3,567,763; polyisocyanate reaction products with acetals according to German Pat. No. 1,072,385; polyisocyanates prepared by telomerization reactions as described in Belgian Pat. No. 723,640; polyphenyl-polymethylene polyisocyanates as described in British Pat. Nos. 874,430 and 848,671; polyisocyanates which contain carbodiimide groups as described in German Pat. No. 1,092,007; perchlorinated arylpolyisocyanates such as those described, e.g, in German Pat. No. 1,157,601; polyisocyanates which contain allophanate groups as described, e.g., in British Pat. No. 994,890 and in Belgian Pat. No. 761,628; and the diisocyanates described in U.S. Pat. No. 3,492,330; polyisocyanates which contain biuret groups as described, e.g., in German Pat. No. 1,101,394; in British Pat. No. 889,050; and in French Pat. No. 7,017,514; polyisocyanates which contain isocyanurate groups as described, e.g., in German Pat. Nos. 1,022,789 and 1,027,394; and in British Pat. Nos. 1,091,949, 1,267,011 and 1,305,036; polyisocyanates which contain acylated urea groups according to U.S. Pat. No. 3,517,139; and polyisocyanates which contain urethane groups as described, e.g., in Belgian Pat. No. 752,261; or in U.S. Pat. No. 3,394,164. Mixtures of the above-named polyisocyanates may be used. Organic polyisocyanates which are modified with ionic groups, for example, with carboxyl and/or carboxylate groups and/or sulphonic acid groups and/or sulphonate groups may be used with the polyisocyanates in this invention. Polyisocyanates may be reacted with alkali metal silicates such as sodium metasilicate pentahydrate, potassium metasilicate pentahydrate, dry grandular crude sodium silicate, and dry granular lithium silicate to produce polyisocyanate alkali metal silicate prepolymer with terminal isocyanate groups or terminal alkali metal silicate groups and may be used with the polyisocyanates in this invention. The polyisocyanate is mixed with the dry granular alkali metal silicate, then heated to 30.degree. C. to 40.degree. C. while agitating at ambient pressure for 10 to 30 minutes, thereby producing a polyisocyanate prepolymer. Any of the suitable non-ionic hydrophilically modified organic polyisocyanates may be used in this invention.

Suitable polyisocyanates such as the aromatic diisocyanates may be reacted with organic compounds which contain at least two hydrogen atoms capable of reacting with isocyanates, preferably with a molecular weight of, generally, from 300 to about 10,000 and in the ratio of from 50-99 mols of aromatic diisocyanates with 1 to 50 mols of said organic compounds to produce isocyanate-terminated reaction products. It is preferred to use polyols (organic polyhydroxyl compound), in particular, compounds and/or polymers 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 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. Compounds which contain amino groups, thiol groups or carboyxl groups may be used. Polyhydroxyl compounds (polyols) which already contain urethane or urea groups, modified or unmodified natural polyols, e.g., castor oil, carbohydreates and starches, may also be used. Additional products of alkylene oxides with phenolformaldehyde resins or urea-formaldehyde resins are also suitable for the purpose of the invention. Polybutadiene polymers with free hydroxyl groups, polysulfide polymers, polybutadienestyrene copolymers and butadiene-acrylonitrile copolymer chains are also suitable for the purpose of the invention.

Polyesters (polyols) containing hydroxyl groups may be, for example, reaction products of polyhydric alcohols, preferably dihydric alcohols and polybasic, preferably dibasic, carboxylic acids. The corresponding polycarboxylic acid anhydride or corresponding polycarboxylic acid esters of lower alcohols or their mixture may be used instead of the free polycarboxylic acids 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, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethylterephthalate and bis-glycol terephthalate. Any suitable polyhydric alcohol (Polyol) 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, neopentyl glycol, cyclohexanedimethol-(1,4-bis-hydroxy-methylcyclohexane), 2-methyl-propane-1,3-diol, glycerol, trimethylol propane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, glucose, starches, fructose, cane sugar, dextrines, castor oils, methylglycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropyleneglycol, polypropylene glycols, dibutylene glycol and polybutylene glycols. The polyesters may also contain a proportion of carboxyl end groups. Polyesters of lactones, such as E-caprolactone or hydroxycarboxylic acids, such as W-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 invention, are known and may be prepared, e.g., by the polymerization of epoxides, e.g., ethylene oxide, propyleneoxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, each with itself, e.g., in the presence of BF.sub.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, trimethylol propane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine or ethylenediamine. Sucrose polyethers such as those described, e.g, in German Pat. Nos. 1,176,358 and 1,064,938 may also be used according to this invention. It is frequently preferred to use polyethers which contain predominantly primary OH groups (up to 90% by weight, based on the total OH group content of the polyether). Also suitable are polyethers modified with Vinyl polymers such as those which may be obtained by polymerizing styrene or acrylonitrile in the presence of polyethers (U.S. Pat. Nos. 3,383,351; 3,304,273; 3,525,093 and 3,110,695; and German Pat. No. 1,152,536) and polybutadienes which contain OH groups.

"Polythioethers" mean, in particular, the condensation of products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. The products obtained are plythio-mixed ethers, polytheiether esters or polythioether ester amides, depending on the co-component.

The polyacetals used may be, for example, the compounds which may be obtained from glycols, e.g., diethylene glycol, triethylene glycol (4,4'-dihydroxydiphenyldimethylmethane), 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 known kind, e.g., those 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., diphenylcarbonate or phosgene.

The 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.

Examples of these compounds which are to be used, according to the invention, have been described, e.g., in High Polymers, Volume XVI, "Polyurethanes, Chemistry and Technology", published by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32 to 42 and pages 44 to 54 and Volume II, 1964, pages 5 and 6 and pages 198 and 199; and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 45 to 71.

Suitable modified organic polyisocyanates, as well as their propolymers, especially those based on aromatic polyisocyanates, can also be subsequently modified to give ionic groups, for example, by reaction with sulfones, beta-lactones, and by grafting on acrylic acid, methacrylic acid or crotonic acid, for example, or by sulphuric acid, chlorosulphonic acid, oleum or sulphur trioxide and then used in the invention. In particular, organic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and the known phosgenation products of the condensation products of aromatic monoamines, especially aniline and aldehyde, especially formaldehyde which is reacted with sulphuric acid, oleum or sulphur trioxide, may be used in this invention. Sulphonated polyisocyanates of this kind which generally still contain ureadione, urea and biuret groups and, in particular, where polyol modification has been carried out before sulphonation, urethane and/or allophanate groups which are formed through secondary reactions during sulphonation are, therefore, particularly preferred as polyisocyanates containing ionic groups. The NCO terminated prepolymers used, for example, for the production of aqueous polyurethane dispersions (U.S. Pat. No. 3,756,992) can be used for the process according to the invention.

Component C

Component C contains organic amphiphilous compounds, preferably containing from 1 to 9 carbon atoms, and has a molecular weight of from 12 to about 400, preferably from 32 to 150, which contain one OH group and/or at least one other hydrophilic and/or polar group. The other hydrophilic and/or polar group is, preferably, a functional group corresponding to one of the following general formulae: RSH, RCH.sub.2 Cl, RCH.sub.2 Br, RCH.sub.2 l, RCN, RNO.sub.2, RCOCl, ROCBr, RSO.sub.2 Cl, RCOOH, RSO.sub.3 H, RCOO.sup.-, RSO.sub.3.sup.-, ROR, ##STR1## wherein R denotes a methyl, ethyl or propyl group. The organic amphiphilous compounds of Component C may contain an OH group and/or from 1 to 6, preferably 1 or 2, of these other functional groups.

The following are examples of Component C:

1. Alcohols, thioalcohols, phenols and thio phenols;: Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butyl alcohol and the isomeric pentanols, hexanols and heptanols, cyclohexanol, methylcyclohexanol, allyl alcohol, methallyl alcohol, cyclohexano-methanol, benzyl alcohol, butylmercaptan, phenols, e.g., phenol and the cresols, thiophenols and thiocresols; also alcohols with from 1 to 4 carbon atoms are preferred, particularly methanol.

2. Aldehydes: Formaldehyde, acetaldehyde, propionaldehyde, butyl aldehyde, pentanals, hexanals, heptanals, octanals and their simple substitution products, semi-acetals and full acetals.

3. Carboxylic acids: Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexane carboxylic acid, heptane carboxylic acid, cyclohexane carboxylic acid, benzoic acid, toluic acid.

4. Carboxylic acid chlorides, carboxylic acid bromides, sulphonic chlorides; Acetyl chloride, propionic acid chloride, acetyl bromide, acid chlorides of C.sub.4 -C.sub.6 monocarboxylic acids, but also methanesulphonic acid chloride, benzenesulphonic acid chloride, p-toluenesulphochloride, o-toluenesulphochloride, carbamic acid chlorides, e.g., t-butyl carbamic chloride, and phenylcarbamic chloride.

5. Esters: Methyl acetate, ethyl acetate, propylacetate, butyl acetate, amyl acetate, the methyl and ethyl esters of propionic, butyric, pentanoic, hexanoic and heptanoic acid and the corresponding isomeric compounds, for example, isobutyric acid and 2,4,6-tribromophenylacetate.

6. Ethers and thioethers: Methyl ethyl ether, cyclohexyl methyl ether, methyl butyl ether, phenol methyl ethyl, thiophenol methyl ether, cresol methyl ether, tetrahydrofuranomethyl-methyl ether.

7. Halomethyl compounds: Ethyl chloride, ethyl bromide, ethyl iodide, n-propylchloride, n-propylbromide, n-propyliodide, isopropyl chloride, isopropyl bromide, isopropyl iodide, butyl chloride, butyl bromide, butyl iodide, C.sub.3 -C.sub.6 -halogenated methyl compounds, benzylhalides, e.g., benzylchloride or benzylbromide, hexahydrobenzyl halides, e.g., cyclohexanomethyl chloride, epichlorohydrin, 2-ethyl-2-chloromethyloxetane and 2-ethyl-2-chloromethyloxetane. Halogenated methyl compounds which contain from 4 to 7 carbon atoms are preferred.

8. Ketones: Methyl ethyl ketone, methyl-isopropyl ketone, methylisobutyl ketone, methyl-isoamyl ketone, methyl-n-propylketone, methyl-n-butyl ketone, methyl-t-butyl ketone, methyl-furanyl ketone, methyl-tetrahydrofuranyl ketone, methylheptyl ketone, ethylhexyl ketone, acetophenone, N-chloroacetophenone and propiophenone.

9. Nitriles: Acetonitrile, propionitrile, butyronitrile, tolunitrile, hexahydrobenzonitrile, acryllonitrile, allylnitrile, methallynitrile, methacrylonitrile.

10. Nitro compounds: Nitromethane, nitroethane, nitrohexane, nitrobenzene, chlorinated nitrobenzenes, nitrocyclohexanes, brominated nitrobenzenes, benzyl nitrate and nitrotoluene.

11. Sulphonic acids: Methanesulphonic acid, ethanesulphonic acid, butanesulphonic acid, benzenesulphonic acid, 2-toluenesulphonic acid, 4-toluenesulphonic acid, chlorosulphonic esters and sulphonic acid esters, e.g., methanesulphonic acid, methyl ester, methane sulphonic acid ethyl ester and chlorosulphonic acid methyl ester.

The carboxyl acids and/or sulphonic acids may be partially or completely neutralized, for example, with alkali metal and alkaline earth metal hydroxides, e.g., sodium hydroxide, potassium hydroxide, barium hydroxide or magnesium hydroxide; or by the addition of amines, e.g., trimethylamine, triethylamine, methylmorpholine, pyridien, dimethylaniline or metal alcoholates, e.g., sodium t-butanolate or potassium isopropanolate. Metal oxides, hydroxides or carbonates, either in the solid form or suspended in diluents may also be used for neutralization. Calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate and dolomite, for example, are particularly suitable. Tertiary amines are useful in this neutralization, e.g., alkoxylated products of primary and secondary amines, and also polyesters or polyacrylates which contain tertiary nitrogen atoms as well as the known condensation products based on epichlorohydrin and polyamines.

12. Components C, according to this invention, may also comprise compounds which contain phosphorus, for example, trimethyl phosphite, trimethylphosphates, triethylphosphite, triethylphosphate, diethylphosphite, diethylphosphate, dimethylphosphite, dimethylphosphate, thiophosphoric acid-O, O-dimethylester, thisphosphoric acid trimethylester, or thiophosphoric acid-O, O-dimethylester chloride.

13. Lignin: Calcium lignosulfonate, lignosulfonic acid sodium salts, lignosulfonic acid, lignin sulfate produced by the alkali process (Kraft's process) and, particularly, de-sulfonated lignin.

Component D

Component D contains the curing agent and/or activators. The following are examples of Component D:

1. Water

2. Water containing 10% to 70% by weight of an alkali metal silicate, such as sodium and/or potassium silicate. Crude commercial alkali metal silicate may contain other substances, e.g., calcium silicate, magnesium silicate, borates or aluminates and may also be used. The molar ratio of Ml.sub.2 OSiO.sub.2 (Ml=metal) is not critical and may vary within the usual limits, but is, preferably, between 4 to 1 and 0.2 to 1.

3. Water containing 20% to 50% by weight of ammonium silicate.

4. Water containing 5% to 40% by weight of magnesium oxide in the form of a colloidal dispersion.

5. Alkali metal metasilicate pentahydrate such as sodium, commercial dry granular sodium, potassium silicate and potassium metasilicate pentahydrate.

6. Water containing 20% to 70% by weight of silica sol.

7. Water containing 0.001% to 10% by weight of an activator (catalyst) such as:

(a) tertiary amines, e.g., triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, N,N,N',N-tetramethylethylenediamine, 1,4-diazo-bicyclo-(2,2,2)-octane, N-methylmethyl-N'-dimethylaminoethyl piperazine, N,N-dimethylbenzylamine, bis (N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethylbeta-phenylethylamine and 1,2-dimethylimidazole. Suitable tertiary amine activators which contain hydrogen atoms which are reactive with isocyanate groups include, e.g., triethanolamine, triisopanolamine, N,N,N',N'-dimethylethanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine and their reaction products with alkylene oxides, e.g., propylene oxide and/or ethylene oxide.

(b) Organo-metallic compounds, preferably organo-tin compounds such as tin salts of carboxylic acids, e.g., tin acetate, tin octoate, tin ethyl hexoate, tin laurate and the dialkyl tin salts of carboxylic acids, e.g., dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or diocyl tin diacetate.

(c) Silaamines with carbon-silicon bonds as described, e.g., in British Pat., No. 1,090,589, may also be used as activators, e.g., 2,2,4-trimethyl-2-silamorpholine or 1,3-diethylaminomethyl-tetramethyldisiloxane.

(d) 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, on pages 96 and 102.

8. 0.001% to 10% by weight, based on the reaction mixture, of an activator (catalyst) listed above.

9. Water containing 20% to 70% by weight of a water-binding agent which is capable of absorbing water to form a solid or a gel, such as hydraulic cement, synthetic anhydrite, gypsum or burnt line.

10. Water containing 1% to 10% by weight of bases which contain nitrogen such as tetraalkyl ammonium hydroxides.

11. Water containing 1% to 10% by weight of alkali metal hydroxides such as sodium hydroxide, alkali metal phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate.

12. Water containing sodium polysulfide in the amount of 1% to 10% by weight.

Surface-active additives (emulsifiers and foam stabilizers) may also be used, according to the invention. Suitable emulsifiers are, e.g, in the sodium salts of ricinoleic sulphonates or of fatty acids or salts of fatty acids with amines, e.g., oleic acid diethylamine or stearic acid diethanolamine. Other surface-active additives are alkali metal or ammonium salts of sulphonic acids, e.g., dodecyclbenzene sulphonic acid or dinaphthyl methane disulphonic acid; or of fatty acids, e.g., ricinoleic acid; or of polymeric fatty acids.

The foam stabilizers used are mainly water-soluble polyester siloxanes. These compounds generally have a polydimethylsilioxane group attached to a copolymer of ethylene oxide and propylene oxide. Form stabilizers of this kind have been described, e.g., in U.S. Pat. No. 3,629,308. These additives are preferably used in quantities of from 0% to 20% by weight, based on the reaction mixture.

Negative catalysts, for example, substances which are acidic in reaction, e.g., hydrochloric acid or organic acid halides, known cell regulators, e.g., paraffins, fatty alcohols or dimethyl polysiloxanes, pigments or dyes, known flame retarding agents, e.g., tris-chlorethylphosphate or ammonium phosphate and polyphosphates, stabilizers against aging and weathering, plasticizers, fungicidal and bacteriocidal substances and fillers, e.g., barium sulphate, kieselguhr, carbon black or whiting, may also be used, according to the invention.

Further examples of surface-active additives, foam stabilizers, cell regulators, negative catalysts, stabilizers, flame-retarding substances, plasticizers, dyes, filler, fungicidal and bacteriocidal substances; details about methods of using these additives, and about their action, may be found in Kunststoff-Handbuch, Volume VI, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966, on pages 103 to 113. The halogenated paraffins and inorganic salts of phosphoric acid are the preferred fire-retardant agents.

According to the invention, it has been further found that it is favorable to carry out the reaction in the additional presence of a compound acting as hardening agent and lowering the pH of the reaction mixture. Suitable compounds of this type include, depending on the reaction mixture employed, ammonium chloride, barium chloride, barium nitrate, bleaching earths, disodium phosphate, calcium-magnesium carbonate, calcium bromide, calcium chloride, calcium iodate, potash alum, potassium fluoride, potassium borofluoride, potassium bromide, potassium carbonate, potassium metabisulfite, potassium silicofluoride, magnesium carbonate, magnesium fluoride, magnesium oxide, magnesium phosphate, monoammonium phosphate, monosodium phosphate, sodium antimonate, sodium acetate, sodium bichromate, sodium bifluoride, sodium bisulfate, sodium bromide, sodium fluoride, sodium hexametaphosphate, tetrapotassium pyrophosphate, zinc acetate, zinc carbonate and boric acid. The hardening agent may be added to Components C or D in an amount sufficient to lower the pH to 7 to 8.

SUMMARY OF THE INVENTION

I have discovered that an alkali metal cellulose silicate condensation product, an organic polyisocyanate and an amphiphilous organic compound will react chemically to produce a polyisocyanate silicate plastic product.

The preferred method is to react a polyisocyanate and/or isocyanate-terminated polyurethane prepolymer of Component B with an alkali metal cellulose silicate polymer of Component A to produce a polyisocyanate silicate prepolymer and/or polyurethane silicate prepolymer which is then reacted with an organic compound (or mixture thereof) of Component C, and optionally, a curing agent and/or an activator of Component D to produce a polyisocyanate organic silicate solid or cellular solid product.

The proportion, by weight, of Component D when used with Component B is preferably from 1:70 to 80:20, and the quantity of Component C is from 1% to 30% by weight, preferably from 2% to 20% by weight, based on Component B. The proportion is 2 parts by weight of Component A to 1 to 10 parts by weight of Component B. An excess of oxidated silicon compound may be used in the production of Component A and used as a filler.

In an alternate method, the Components A, B, C and, optionally, D, are added simultaneously and mixed homogeneously, and in a short period of time (a few seconds to about 10 minutes), the chemical reaction begins and a solid or cellular solid product is produced.

In another alternate method, the Components A, B, C and a polyol are added simultaneously and mixed homogeneously, and within a few second to 10 minutes, the mixture reacts chemically to produce a solid or cellular solid product.

The polyisocyanage may be first reacted with an oxidated silicon compound to produce a polyisocyanate prepolymer which is then reacted with Components A, C and, optionally, D, to produce a solid or cellular solid product.

Mixtures which contain more than 30% by weight of water are usually soft, solid products which may be used as putties, surface coatings, adhesive bonds, grouting compositions, caulking compositions and may be used for producing foams by adding a blowing agent. The blowing agents are usually inert liquids with boiling points ranging from -25.degree. C. to 80.degree. C.

The blowing agents used may be, e.g., acetone, ethyl acetate, methanol, ethanol, halogenated alkanes, e.g., methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether. Compounds decompose at temperatures above room temperature with liberation of gases, e.g., nitrogen, such as azo compounds, azoisobutyric acid nitrile, may also act as blowing agents. Other examples of blowing agents and details about the use of blowing agents are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966, on pages 108 and 109, 453 to 455 and 507 to 510.

The proportions of the components may be adjusted to obtain the desired product, ranging from a solid to a highly cellular solid. When water is used, it reacts with the NCO group to produce CO.sub.2 and pores are produced in the product by the evolved CO.sub.2. In certain cases, the CO.sub.2 is rapidly evolved and escapes before the product hardens so that a solid product can be produced nearly completely free of air cells. The hardening times generally increase with decreasing proportions of Component C.

Powdered calcium, magnesium, aluminum or zinc may be used and will react with the alkali metal ions to bring about the evolution of hydrogen which acts as a blowing agent. Compressed gases such as air, nitrogen, methane, etc., may be mixed in the components and may also be used to mix components, then be used as the blowing agent. These metal powders also have a hardening and reinforcing effect.

The properties of the foams (cellular solids) obtained from any given formulation, e.g., their density in the moist state, depends, to some extent, on the details of the mixing process, e.g., the form and speed of the stirrer and the form of the mixing chamber, and also the selected temperature at which foaming is started. The forms will usually expand from 3 to 12 times the