EP0044832A4

EP0044832A4 - Production of poly(polyisocyanate silicate)solid or cellular solid utilizing alkali metal silicates.

Info

Publication number: EP0044832A4
Application number: EP19800900962
Authority: EP
Inventors: David H Blount
Original assignee: Individual
Current assignee: Individual
Priority date: 1980-02-04
Filing date: 1980-04-14
Publication date: 1982-07-06
Also published as: WO1981002300A1; NL8020181A; EP0044832A1; SE8105379L; GB2082611A

Description

PRODUCTION OF POLY (POL ISOCYA ATE SILICATE) SOLID OR CELLULAR SOLID UTILIZING ALKALI METAL SILICATES

TECHNICAL FIELD

This invention relates to a process for the production of poly (polyisocyanate alkali metal) prepolymer by reacting a poly- isocyanate chemically with an alkali metal silicate by mixing them and then heating the mixture thereby producing a poly (polyisocyanate alkali metal) prepolymer. The poly (poly¬ isocyanate alkali metal silicate) prepolymer is cured with heat or a curing catalyst such as water.

DISCLOSURE OF THE INVENTION

This invention relates to a process for the producing of poly (polyisocyanate silicate) solid or cellular solid by reacting a polyurethane compound with an alkali metal silicate to pro¬ duce a poly (polyisocyanate alkali metal silicate) prepolymer. The prepolymer may be cured by heating or adding a curing agent. The products produced by this process may be quite varied in physical properties; they may be solid or porous, rigid or elastomeric, and the porous products may be rigid or soft and flexible.

The products produced by this invention may be utilized as thermal insulating material, noise insulating material, flotation material in boats, shock-resistant packaging, cushions, as fiber, as coating agents, as fillers, as impregnating agents, as adhesives, as casting material, as putty material, as construc¬ tional components of a building, etc. The products have improved heat and flame resistant properties. The products are novel and economical. Some of the products have a number of woodlike physical properties-

The reaction of alkali metal silicates and mono-alkali metal silicates with polyisocyanates to produce polyurethane-silicate resins and forms were listed in U.S. Patent Application No. 71,628 filed September 11, 1970, by David H. Blount, now abandoned. The alkali metal silicates, mono-alkali metal silicates a mixtures thereof, may be produced by any of the methods common known in the arts. A useful mixture which contains alkali met silicate and predominately mono-alkali metal silica may be produced by heating 1 to 2 mols of an alkali metal hydroxide w about 1 mol of fine granular silica in water at 80 to 100 C, while agitating at ambient pressure for 20 to 60 minutes until the water evaporates. Mono-alkali metal silicate may also be produced by heating 1 mol of hydrated silica with 1 mol of alk metal hydroxide compound in water until the water is evaporate It is preferred that the alkali metal silicate be in a granula form.

The poly (polyisocyanate silicate) solid or cellular soli products may be modified or improved by adding organic compoun inorganic compounds, and/or organic-silicate compounds. These compounds may be added before the isocyanate and the alkali si cate are reacted together or they may be added after a poly (polyisocyanate silicate) prepolymer is produced. Organic poly polyesters, polyether glycols and polysulfides, polybutadiene, butadiene-styrene copolymers and butadieneacrylonitrile which contain free hydroxyl groups may be used in this invention.

U. S. Patent No. 4,072,637 and U. S. Patent Application No. 663,924, filed on March 4, 1976, by David H. Blount utiliz silicon acids to react with polyisocyanates to produce poly (polyisocyanate silicate) resins and foams.

Various alkali metal silicate compounds may be used in this invention such as sodium, potassium and lithium silicates. Other alkali metal silicates may be used. Sodium silicate and mono-sodium silicate are preferred alkali metal silicates beca of their low cost and ready availability. The cost is further lowered by using a considerable amount of water as a curing catalyst which is utilized in the product. The crude commerci alkali metal silicates may contain other substances such as calcium silicate, magnesium silicate, aluminates or borates may also be used. The molar ratio of Me-.0/Si0_(Me = metal) is not critical and may vary from 4 to 1 and 0.1 to 1.

OMPI ^■ Any suitable polyisocyanate may be used in this invention. For example, arylene polyisocyanates such as tolylene, meta- phenylene, 4-chlorophenylene-l, 3-, methylene-bis (phenylene-4-) , biphenylene-4,4'-, 3,3'-dimethoxy-biphenylene-4,4'-, 3,3'- diphenylbiphenylene-4,4'-, napthalene-1,5-, and tetrahydron- aphthalene-1, 5-diisocyanates and triphenylmethane tri- isocyanate, alkylene polyisocyanates such as ethylene, ethylidene, 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. Polyisothiocyanates, inorganic polyisothiocyanates, polyisocyanates which contain carbodi- imide groups as described in German Patent 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 poly (polyisocyanate silicate) solid or cellular solid. Mixtures of the above mentioned poly¬ isocyanates may be used.

It is generally preferred to use commercial, readily avail¬ able polyisocyanates such as toluene-2,4- and -2,6, diisocyanate and any mixture of these isomers ("TDI") , ("crude MDI") , polyphenyl-polymethylene-isocyanates obtained by anilineformal- dehyde condensation followed by phosgenation, and modified polyisicyanates which contain carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, imide groups or biuret groups.

The alkali metal silicate and/or mono-alkali metal silicate in the amount of 0.1 mol to 2 mols may react with 1 mol of the polyisocyanate compound by mixing at ambient tempera¬ ture to 45 C. , preferably to 30° to 40° C. , while agitating for 10 to 30 minutes, thereby producing yellow granules of a poly (polyisocyanate alkali metal silicate) prepolymer. The prepolymer may be cured by heating above 50 C. or by adding a curing agent such as water, and a solid or cellular solid product is produced. Various polyols may be added to the alkali metal silicate before the polyisocyanate is added or after the poly (polyisocyanate alkali silicate) prepolymer is produced- Any suitable polyol may be used in this invention such as glycerol glycerol monochlorohydrin, ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol triethylene glycol, dipropylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, ether glycols, bispherol A, resorcinol, bis(bet -hydroxyethyl) terephthalate, 2-ethyl-2-(hydroxy ethyl)-1,3-propanediol, pentaerythritol, trimethol propane; trimethol ethane, 2,2-osydiethanol, quinito mannitol, sorbitol, methylglucoside, glucose, starches, tri- methylol ethane, trimethylol propane, hexane-1, 2,6-triol, butane-1,2,4-trill, 1,8-octanediol, fructose, cane sugar, molasses, dextrines, corn syrup, maple syrup, castor oil, dibutylene glycol, polybutylene glycol, polyester resins with free hydroxyl groups, polycarbonates which contain hydroxyl groups and mixtures thereof.

Various polyesters containing free hydroxyl or carboxyl end groups may be used. Polyesters of lactones, such as E-caprolactone, polyesters of hydroxycarboxylic acids, such as W-hydroxy-caproic acid may be used. The hydroxyl group containing polyesters may be produced by reacting polyhydrix alcohols, preferably dihydric alcohols with addition of trihydric alcohols as desired, and polybasic carboxylic acids wuth dibasic carboxylic acids being preferred. The corres¬ ponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures may be used for preparing the polyesters in place of or com¬ bined with the free polycarboxylic acids. The polycarboxylic acids may be aliphatic, cycloalipathic, aromatic and/or heterocyclic and may be substituted, e.g., with halogen atoms, and may be unsaturated. Any suitable compound such as adipic acid, azaleic acid, succinic acid, suberic acid, sebaci acid, phthalic acid, isophthalic acid, trimellitic acid, maleic acid, fumaric acid, dimeric and trimeric fatty acids

OM

^■* (such as oleic acid mixed with monomeric fatty acids) , phthalic acid anhydride, tetrahydrophthalic acid anhydride, tetrach- lorophthalic acid anhydride, hexahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, maleic acid anhydride, glutaric acid anhydride, bis-glycol terephthalate, dimethylterephthalate and mixtures thereof may be reacted with the listed polyols to produce polyester which may be used in this invention. The production of polyesters is commonly known in the arts.

The polyesters with 2 to 8 hydroxyl groups may be prepared by the polymerization of epoxides such as ethylene oxide,pro- pylene oxide, butylene oxide, tetrahydrofuran. styrene oxide or epichlorohydrin, each with itself or by addition of these epo- xides or mixtures thereof with alcohols or amines. Polyethers may be modified with vinyl polymers such as styrene or acrylo- nitrile.

Various polyacetals, polythioethers, polyester amides, polyamides, polyhydroxyl compounds which already contain urethane or urea groups, modified or unmodified natural polyols, addi¬ tion products of aϊkylene oxides with phenolformaldehyde resisn or with urea-formaldehyde resins may be used in this invention and added with the alkali metal silicates or after the poly (polyisocyanate alkali metal silicate) prepolymer is produced. These polymers may be added in the amount from 0% to 100% -by weight, based on the weight of polyisocyanate.

Examples of these compounds which -are to be used according to this invention have been described, e.g., in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology," published by Saunders-Frisch, Interscience Publishers, New York, London. Vol. I, 1962, pages 32 to 42 and pages 44 to 54 and Vol. II, 1964, pages 5 to 6 and pages 198 to 199.

The preferred methods to produce poly (polyisocyanate silicate) solid or cellular solid products is to mix about 1 part by weight of a fine granular alkali metal silicate with 0.5 to 6 parts by weight of a polyisocyanate or polyisothiocyanate. Then heat the mixture to 30° to 40° C while agitating at ambient pressure, for 10 to 30 minutes, thereby producing yellow gran¬ ules of poly (polyisocyanate alkali metal silicate) prepolymer.

Then when desirable, the prepolymer is heated to 50° to while agitating at ambient pressures and it begins to expand immediately to about 3 to- 12 times its original volume to prod a rigid, self-standing poly (polyisocyanate silicate) cellular solid.

A curing agent may be added to the poly (polyisocyanate alkali metal silicate) prepolymer in the amount of 0.001 to 10% by weight, based on the reactants, instead of heating. The curing agent is thoroughly mixed with the prepolymer, then it rapidly expands 3 to 12 times its original volume to produc a rigid, self-standing poly (polyisocyanate silicate) cellular solid.

In an alternate method, about 1 part, by weight of a fine granular alkali metal silicate and 0.5 to 6 parts by weight of a polyisocyanate are mixed then heated to 50 to 80 C whil agitating at ambient pressure. The mixture begins to expand when the temperature reached 50 to 80 C and it expands 3 to 12 times its original volume to produce a rigid, self-standing poly (polyisocyanate silicate) cellular solid product.

In another alternate method, a curing agent is added to the mixture of alkali metal silicate and polyisocyanate. Then, the mixture is agitated at ambient pressure. In a few minutes (1 to 15 minutes) the mixture expands 3 to 12 times its origin volume to produce a poly (polyisocyanate silicate) cellular solid or is cured into a solid product.

Polyols in the amount of 0.1 to 3 parts by weight may be reacted chemically with 1.5 to 7 parts by weight of poly (polyisocyanate alkali metal silicate) prepolymer to produce poly (urethane silicate) solid or cellular solid products. The polyols may also be mixed with the alkali metal silicate and polyisocyanate simultaneously to produce poly (urethane silicate solid or cellular solid products.

Various suitable vinyl monomers may be chemically reacted with the poly (polyisocyanate alkali metal silicate) prepolyme alkali metal silicate and polyisocyanate mixture, alkali metal silicate, listed organic compound and polyisocyanate mixture or alkali metal silicate, polyol and polyisocyanate mixture to produce poly (urethane silicate) solid or cellular solid products. Various suitable vinyl monomers may be used such as acrylonitrile, vinyl acetate, styrene, methyl styrene, 1,1'_ dichloroethylene, n-vinyl-2-pryrollidone, vinyl toulenes, n-vinyl carbazone, 2-vinyl pyridine, 4-vinyl prydine, vinyl alkyl ethers, allyl vinyl ethers, alicyclic ethers, aryl alkyl vinyl ethers, aryl vinyl ethers, divinyl benzene acrylic acid, hydroacrylic acid, methacrylic acid, ethyl acrylic acid, crotnoic acid, chloracrylic acid, fluoroacrylic acid, cyclo- hexyl methacrylic acid, isobutyl methacrylic acid, bromoacrylic acid, benzyl acrylic acid, methyl methacrylate, propyl acrylate, butyl acrylic acid, propyl acrylate, butyl acrylate, pentadecyl acrylate, hexadecyl acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl ethyl acrylate, ethyl methacrylate, methyl alphachloroacrylate, 2-chloroethyl acrylate, 1,1-dihydroper- fluorobutyl acrylate, lauryl acrylate, cyclohexyl-cyclohexyl methacrylate, allyl methcrylate, ethylene methacrylate, n- butyl methacrylate, polyethylene glycol dimethecrylate, tetra- ethylene glycol dimethacrylate, and mixtures thereof. The vinyl monomers are added in the amount of 0.1 to 3 parts by weight per 0.5 to 6 parts by weight of the polyisocyanate.

Various suitable allyl type halides may be chemically reacted with the poly (polyisocyanate alkali metal silicate) prepolymer, a mixture of alkali metal silicate and polyisocyanate or a mixture of alkali metal silicate, polyolcate and poly¬ isocyanate to produce poly (urethane silicate) solid or cellular solid products.

Various suitable allyl type halides may be used which have the general formula:

H,C=C-CH X

^~ R

Wherein R is a hydrogen or a C, to C alkyl group and X is chlorine or bromine.

Representative examples of allyl type halides are such compounds as allyl chloride, allyl bromide, crotyl chloride, crotyl iodine, beta- ethylallyl chloride, beta-methylallyl bro¬ mide, methyl vinyl carbinyl chloride, methyl vinyl carbinyl fluoride, alpha-dimethyl-allyl chloride, beta-cyclohexylallyl chloride, cinnamyl chloride, beta-ethylcrotyl chloride, betaphenyl allyl bromide, alpha-dicyclohexylallyl chloride, beta-propyallyl iodide, beta-phenylallyl chloride, beta- cyclohexylallyl fluoride, 2-chloromethyl butane-1, 2-chloro¬ methyl pentene-1, 2-chloromethyl hexene-1, and mixtures thereo

Plasticizers, fillers, curing rate modifiers, pigments; extenders and the like may be added to the mixtures in this invention or may be added to the prepolymers at the time of curing and may be in the amount from 5% to 50% by weight, base on the weight of the prepolymer or mixture. Plasticizers may include benzoate esters, dipropylene glycol benzoate, dodecyl phthlate and propylene glycol phthalate. Extenders such as high boiling coal tar distillates, mineral oil, poly (alpha- methylstyrene) polymers, mercapto-terminated liquid polysulfid polymers, paraffin oil and sulphonated castor oil may be used. Finely divided fillers such as alkali metal silicates, ammoniu silicate, metal oxides, metal hydroxides, metal carbonates, chalk, heavy spar, gypsum, anhydrite, and mixtures thereof may be used in this instant invention.

In the production of certain foams, it is advisable to ad blowing agents. These are liquids with boiling points, rangin from -25 to 80 C. and preferably from -15 to 40 C. The organic blowing agents are used in quantities of from 2% to 30% by weight, based on the reaction mixture. The organic blowing agents such as acetone, ethyl acetate, halogenated alkanes, e.g. methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane; also butane, hexane, heptane, diethylether, compounds which decompose at temperature above room temperatures with liberation of gases, e.g. nitrogen, such as azo compounds and azoisobutyric acid nitrile may be used in this process. Fine metal powders, e.g. calcium, zinc, magnesium and aluminum will act- as blowing agents by producing hydrogen in an alkaline solution. Other curing agents or catalysts combined with water or in place of water may be utilized as the catalyst to produce foam products from the poly (polyisocyanate alkali metal silicate) prepolymers, and alkali metal silicate and polyisocyanate mixtures. These catalysts are commonly known in the arts such as tertiary amines, siloamines, basic compounds which contain nitrogen, e.g. tetra-alkylammonium hydroxide, alkali metal phenolates, alkali metal alcolates, hexahydrotriazines, tin organo-metallic and mixtures thereof. These catalysts are generally used in a quantity of from 0.001% to 10% by weight, based on the weight of the reaction mixtures-

Suitable foam stabilizers are mainly water-soluable poly- ether siloxanes and those described in U. S. Patent No. 3,629,308. These additives are preferably used in quantities of from 0% to 20% by weight, based on the reaction mixture.

Further examples of surface active additives, foam stabi¬ lizers, cell regulators, negative catalysts, stabilizers flame retarding substances, plasticizers, dyes, fillers and fungici- dal and bacteriocidal substances and details about methods using these additives and their actions may be found in Kunststoff-Handbuch, Vol. VI. published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 103 to 113.

The quantitative proportions of the reactants used in this invention are not critical, and exact measurements are not necessary. The amount of any of the reactants may vary. In the production of poly (polyisocyanate silicate) solid or cellu¬ lar product and poly (polyisocyanate organic-silicate) solid or cellular solid products, a thick liquid or soft solid propolymer may be produced when an excess of alkali metal silicate and an organie compound is used. The prepolymer may be further reacted with the polyisocyanate, to produce a solid or cellular solid product. The soft solid prepolymer may be used as putty, for surface coating, or adhesive bonds, grouting compositon and for producing foams. It may also be injection molded, extruded^" or worked- p in a kneader-

When the solid or cellular solid product produced by this invention is to be used where high temperature resistance and complete flame resistance is necessary, it is produced by using a silicate content of 70% to 95% and by using a non-volatile hardner such as mineral acids, hydrogen containing salts, ammo salts, etc. Compressed air may be used as the blowing agent. Flame retarding agents such as halogenated paraffins and inorganic salts of phosphoric acid may be added.

The methods according to this invention are suitable to b performed in the available mechanical devices. The cellular solid products may be carried out by mixing the reactants in one or more steps in a continuous or intermittent operating mixing apparatus. The mixed reactants will expand and produce cellular solid products outside the mixing apparatus.' If desired, prepolymer may be prepared then expanded by heat, curing catalyst, blowing agent or by adding additional polyiso cyanate. The prepolymers of this invention are cured by heati at a temperature from 50 to 200 C. Once the curing reaction started, external heat is not usually necessary to finish the curing process.

In case the desired amount of foaming is not obtained, ho expanded beads of glass or plastic or hollow natural material may be used for producing cellular solid products. The produc of this invention may be produced as cellular solid beads by dropping the curing'mixture into petroleum hydrocarbons or by free fall. These beads may be compressed together or mixed wi other light weight or expanded material, e.g., expanded glass, expanded clay, wood, cork, popcorn, hollow plastic beads^', e.g. beads of polystyrene, polyethylene, polypropylene, polyvinyl chloride, polysulphone/ polyepoxide, polyurethane, urea- formaldehyde, phenol-formaldehyde, polyimide, and added to the mixtures of this invention before curing. The cured product may be used as insulating materials which have good fire re¬ sistant properties, as constructional elements in the building industry, furniture industry and motor vehicle and aircraft industry. The beads or cellular solid products in- crumbly form may be used as a soil conditioner.

The expanding mixtures of this invention may be sprayed o walls, soil banks, fabric, wire meshes, fiberglass cloth and

/-BU f O fibers, walls of caves, mines, tunnels, etc. to form a cellular solid layer for insulation and protection. The expanding mix¬ tures may be used for sealing joints, for sealing and plastering surfaces, for erection of walls and homes, for priming, insula¬ ting and deocrating, for coating as living material, as adhesives, mortars, casting compositions and fillers. The foams will cure and dry on the surface on which they are sprayed.

The expanding mixtures of this invention in many cases may be poured into forms and used in place of wood. The cured product may be sawed, nailed, drilled, planed, ground and treated as wood. The mixtures may be extruded through dies and slots to produce fibers, thin layered sheets and may be used in paper making or as filler in paper making, etc.

Various fillers may be added to the mixture in this inven¬ tion in considerable quantities of fillers without losing their advantageous properties. Fillers in the form of fine particles or powders are preferred such as chalk, dolomite, gypsum, glass, carbon, anhydrite and-the conventional plastics. Other fillers in the form of granulates, wire, fibers, crystallites, rods, spirals, beads, foam particles, woven or knitted fabric, tapes, foil, fillers of solid inorganic or organic substances such as sand, alumina, asbestos, aluminum oxide and hydroxide, zeolites, calcium sulfates, alumino silicate, cements, basalt powder or wood/ glass fibers, carbon fibers, graphite carbon black, Al, Fe, Cu and Ag powders, steel wool, bronze or copper meshes, silicon powder, glass powder, wood chips, wood flower, lignin cork, cotton, straw, popcorn, coke or particles of filled or unfilled, foamed or unfoamed, stretched or unstretched organic polymers may be used. Examples of organic polymers are poly¬ styrene, polyethylene, polypropylene, polyacrylonitrile, poly- butadiene, polyisoprene. polytetrafluroethylene, aliphatic and aromatic polyesters, mela ineurea resins, polyacetal resins, polyethers, polyether silicate polymers, polyureas, polyepoxides, polyhydantoins, polysulphones, polyurethanes, polyimides, polyamides, polycarbonates and any copolymers thereof.

The object of the present invention is to provide a novel method of producing poly (polyisocyanate silicate) solid or

O PI cellular solid products. Another object is to produce novel poly (urethane silicate) solid or cellular solid products. Another object is to produce relative low cost foamed and elastomeric inorganic-organic plastics. Still another object is to produce novel cellular solid products of relatively low cost, rigid, fine cellular, light-weight, high-strength, good flame resistance and dimensional stability when heated. A further object is to produce inorganic-organic plastics that m be used for thermal insulating , structural purposes, sound proofing, shock resistant packaging, cushions, coating wood an metals, adhesives, casting material, putty, etc.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail by the specific examples which follow, it being understood that these preferred embodiments are illustrative of, butnot limited to, procedures which may be used in the production of poly (poly¬ isocyanate silicate) solids or cellular solid products. Parts and percentages are by weight unless otherwise indicated.

Example 1

About 1 part by weight of granular sodijm metasilicate pentahydrate and 1 part by weight of toluene diisocyanate (80% 2,4-isomer and 20% 2,6-isomer) are mixed, then heated to 30 to 40 C. while agitating for 10 to 30 minutes, thereby producing a mixture of poly (toluene diisocyanate sodium silic prepolymer, sodium silicate and toluene diisocyanate. The mixture is then heated to about 50° C. , and the mixture rapidl expands 3 to 12 times its original volume, thereby producing a rigid, self-standing poly (toluene diisocyanate silicate) cellular solid.

Example 2

About 2 parts by weight of granules of potassium meta¬ silicate pentahydrate and 3 parts by weight of toluene diisocyanate are mixed, then heated to 30° to 40° C. while agitating at ambient pressure for 10 to 30 minutes, thereby producing a mixture of poly (toluene diisocyanate potassium silicate) prepolymer, toluene diisocyanate and potassium silicate. The mixture is then heated to about 50 C. while agitating, and the mixture expands rapidly to 3 to 12 times its original volume, thereby producing a rigid self-standing poly(poly¬ isocyanate silicate) cellular solid.

Example 3 ^•

Dry granular hydrated silica is heated with sodium hydro¬ xide in a 1:1 mol ratio and in an aqueous solution until the water evaporates, thereby producing granules of sodium silicate, and monosodium silicate. About 2 parts by weight of this mixture of granules and 2 parts by weight of toluene diisocyanate are mixed, then heated to 30 to 40 C. while agitating at ambient pressure, thereby producing yellow granules of poly (toluene diisocyanate sodium silicate) prepolymer. The pre¬ polymer is then heated to about 50 C. while agitating, and the mixture rapidly expands to 3 to 12 times its original volume, thereby producing a rigid self-standing poly (toluene diisocyanate silicate) cellular solid product.

Example 4

About 1 part by weight of fine granular silica and 1 part by weight of sodium hydroxide are mixed in water, then heated to 80 to 100 C. until the water evaporates, thereby producing a white powder containing predominately mono-sodium silicate and sodium silicate.

About 2 parts by weight of the white powder and 3 parts by weight of toluene diisocyanate (80% 2,4-isomer and 20% 2,6- isomer) are mixed, then heated to 30° to 40° C. while agitating for 10 to 30 minutes, thereby producing poly (toluene diiso- cynate sodium silicate) prepolymer. The prepolymer was then heated to above 50 C. while agitating, and the mixture rapidly expands to 3 to 12 times its original volume, thereby producing a rigid self-standing poly (toluene diisocyanate silicate) cellular product.

Example 5

About equal parts by weight of fine granular silica and sodium hydroxide flakes are mixed in water, then heated at 80° to 100 C. while agitating for 20 to 60 minutes at ambient pressure until the water evaporates, thereby producing a whit granular mixture of sodium silicate and mono-sodium- silicate. About 1 part by weight of the granular mixture of sodium sili cate and mono-sodium silicate. About 1 part by weight of the granular mixture and 2 parts by weight of toluene diisocyanate (80% 2,4-iosmer and 2,6-isomer) are mixed, then heated to abo 50° C. while agitating and the mixture expands rapidly to 3 to 12 times its original volume to produce a rigid self-standing poly (polyisocyanate silicate) cellular solid product.

The following examples, 6 through 17, will utilize 2 part by weight of the mixture of poly (toluene diisocyanate sodium silicate) prepolymer, sodium silicate and toluene diisocyanate as produced in Example 5 mixed with 1 part by weight of the following reactants. The mixture rapidly expands 3 to 12 time its original volume to produce a poly (urethane silicate) pro¬ duct. A curing catalyst in the amount of 1 to 1 part by weigh may be added with the organic reactant,

CURING TYPE OF

EX. REACTANT- AGENT PRODUCT

6 n-vinyl-2-pyrrolidone 0.5 part/water rigid cellular sol

7 1,1-dichloroethylene 0.5 part/water rigid cellular sol and 0.25 part/ ethylene-dramine

' 8 methyl styrene 1 part/water solid

9 methacrylonitrile none rigid cellular sol

10 ethyl acrylic acid none rigid cellular sol

11 vinyl acetate none rigid cellular sol

12 acrylic acid none rigid cellular sol

13 methyl methacrylate 1 part/water solid

14 allyl chloride 0.5 part/water rigid cellular sol

15 acrylonitrile 0.5 part/water rigid cellular sol

16- methallyl chloride 0.5 part/water rigid cellular sol

17 methacrylic acid 0.5 part/water rigid cellular sol

The following Examples, 18 through 27, utilize 1 part by weight of a polypol and the mixture of poly (toluene diisocyanate potassium silicate) prepolymer, potassium silicate and toluene diisocyanate as produced in Example 2. They are mixed with 0 to 1 part by weight of a curing catalyst, and the mixt-ure rapidly reacts chemically to produce a poly (urethane silicate) solid or cellular solid product. Two parts by weight of the mixture of poly (toluene diisocyanate potassium silicate) prepolymer, potassium silicate and diiso¬ cyanate are used.

POLYOL CURING TYPE OF

EX. SILICATE CATALYST PRODUCT

18 glycerol none rigid cellular solid

19 ethylene glycol none rigid cellular solid

20 diprophylene glycol none rigid cellular solid

21 polyethylene glycol none rigid cellular solid (mol. wt. 1000)

22 triethylene glycol none rigid cellular solid

23 polypropylone glycol none rigid cellular solid (mol. wt. 400)

24 propylene glycol none rigid cellular solid

25 polypropylene glycol none rigid cellular solid (mol. wt. 320)

26 mannitol none rigid cellular solid

27 castor oil 00..55 ppaar. t water solid

The following Examples, 28 through 36, utilize 2 parts by weight of the mixture of poly (toluene diisocyanate sodium silicate) prepolymer, sodium silicate and toluene diisocyanate as produced in Example 1 with 1 part by weight of a reactant and 1 part by weight of a polyol. They are mixed and they rapidly expand 3 to 12 times their original volume to produce a poly (urethane silicate) product. TYPE OF

EX. REACTANT POLYOL PRODUCT

28 methallyl chloride 2,2'-oxydiethanol rigid cellular sol

29 allyl chloride glycerol rigid cellular sol

30 1,1"-dichloro- 1,4-butanediol liquid ethylene

31 vinyl acetate glycerol rigid cellular sol

32 chlorostyrene propylene glycol rigid cellular sol

33 acryloni rile ethylene glycol rigid cellular sol

34 acrylic acid polyethylene semi-rigid cellula glycol

35 methyl methacry¬ triethylene rigid cellular sol late glycol

36 styrene 1,6-hexanediol rigid cellular sol

The following Examples, 36 through 50 utilize 2 parts by weight of the poly (toluene diisocyanate sodium silicate) pre¬ polymer as produced in Example 3, 1 part by weight of a vinyl monomer and 1 part by weight of a polyol. They, are mixed and the mixture rapidly expands 3 to 12 times its original volume to produce a poly (urethane silicate) product.

VINYL TYPE OF

EX. MONOMER POLYOL PRODUCT

36 acrylonitrile triethylene glycol rigid cellular sol

37 methyl styrene diethylene glycol soft solid

38 styrene ethylene glycol rigid cellular sol

39 vinyl acetate propylene glycol rigid cellular sol

40 1,1'-dichloro- none soft solid ethylene

41 n-vinyl-2- none solid pyrrolidone

42 n-vinyl-2- glycerol semi-rigid cellula Pyrrolidone solid

43 acrylic acid polypropylene solid

44 methacrylic acid 1,4-butanediol rigid cellular sol

45 methyl methacrylate glycerol rigid cellular sol VINYL TYPE

EX. MONOMER POLYOL PRODUCT

46 methacrylonitrile polyethylene rigid cellular solid glycol

47 hydroacrylic acid pentaerythritol rigid cellular solid

48 isoethyl vinyl starch rigid cellular solid ether

49 ethyl acrylic acid liquid polyester rigid cellular solid resin

50 n-vinyl carbazole trimethylol propane rigid cellular solid

The following Examples, 51 through 62, utilize 2 parts by weight of dry grnaular sodium metasilicate, 2 parts by weight of toluene diisocyanate and 2 parts by weight of an organic reactant and are added at the same time while agitating. They rapidly react to produce a thick liquid or a soft solid with free hydroxyl and silicic acid groups. To these solid prepolymers, 1 part by weight of toluene diisocyanate is added and mixed thoroughly. The mixture expands rapidly to produce a rigid, self-standing poly (polyisocyanate organic-silicate) cellular solid product.

TYPE OF PTS/TOLUENE TYPE OF

EX. RECTANT PRODUCT DIISOCYANATE PRODUCT ADDED

51 1,4-butanediol soft solid 1 rigid foam

52 methyl methacrylate soft solid 1 rigid foam

53 propylene glycol soft solid 1 rigid roam

54 acrylic acid soft solid 1 rigid foam

55 acrylonitrile solid 0 granules

56 styrene rigid foam 0 rigid foam

57 allyl bromide soft solid 1 rigid foam

58 methyl styrene soft solid 1 rigid foam

59 methallyl bromide soft solid 1 rigid foam

60 glycerol soft solid 1 rigid foam

61 allyl chloride soft solid 1 rigid foam

62 methallyl chloride soft solid 1 rigid foam The following Examples, 63 through 81, utilize 1 part by weight of the. poly (toluene diisocyanate sodium silicate) prepolymer as produced by Example 4 which is mixed with 1 par by weight of a rectant and 0 to 2 parts by weight of a curing agent,,thereby producing a poly (urethane silicate) solid or cellular solid product.

CURING TYPE OF

EX. REAC ANT AGENT PRODUCT

63 glycerol none rigid cellular solid

64 ethylene glycol none rigid cellular solid

65 diethylene glycol none rigid cellular solid

66 triethylene glycol none rigid cellular solid

67 polyethylene glycol none semi-rigid cellular solid

68 propylene glycol none rigid cellular solid

69 castor oil 0.5 part/water semi-rigid cellular solid

70 polyethylene glycol 0.5 part/water rigid cellular solid

71 polypropylene glycol none semi-rigid cellular solid

72 trimethylol ethane +1 part/water

73 castor oil none semi-rigid cellular solid

74 glyptal resin none rigid cellular solid

75 1,6-hexanediol none rigid cellular solid

76 adipic acid none rigid cellular solid

77 maleic anhydride none rigid cellular solid

78 phthalic anhydride none rigid cellular solid

79 pentaerythritol none rigid cellular solid

80 dibutylene glycol none rigid cellular solid

81 polybutylene glycol 0 .5 part/water solid

Example 82

Three parts by weight of a mixture of a phosgenation prod of aniline-formaldehyde condensation product and tolylene diisocyanate with an NCO content of about 30 and 2 parts by we of granular sodium metasilicate pentahydrate are mixed then he to^"30 to 40 C while agitating for 10 to 30 minutes, thereby producing poly (polyisocyanate sodium silicate) prepolymer. The prepolymer is then heated to 50 to 80 C. , and the mixture expands 3 to 12 times its original volume thereby producing a rigid, self-standing poly (polyisocyanate silicate) cellular solid.

Example 83 Three parts by weight of a liquid crude phosgenation pro¬ duct of an aniline-formaldehyde condensate, 2 parts by weight of poly (toluene diisocyanate sodium silicate) prepolymer, 2 parts by weight sodium waterglass (40% Na-0. SiO_ = 1:2), 0.01 part by weight of triethylamine, 0.01 part by weight of detergent and 1 part by weight of Portland cement are added and mixed at the same time. The mixture rapidly expands 3 to 12 itmes its original volume to produce a rigid, self-standing poly (polyisocyanate organic-silicate) cellular solid.

The following Examples, 84 to 92 utilizes 3 parts by weight of toluene diisocyanate, 1 part by weight of dry granular sodium silicate, and a polyol listed below, which are mixed simul¬ taneous while agitating at a temperature between ambient and 40° C. for 10 to 30 minutes thereby producing a poly (urethane silicate) prepolymer. The prepolymer is then heated to 50 to 80° c. while agitating until the prepolymer begins to expand. It expands 3 to 12 times its original volume thereby producing a poly (urethane silicate) cellular solid.

AMOUNT IN PARTS

EX. POLYOL BY WEIGHT

84 glycerol 0. .1

85 propylene glycol 0. .2

86 polypropylene glycol (400 mol wt.) 2

87 polyethylene glycol (1500 mol wt.) 3

88 castor oil 1. .5

89 liquid polyester resin with free 3 OH groups

90 starch 2

91 liquid polybutadiene resin 2 .5 with free OH groups.

92 polyether glycol 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 to enhance or otherwise modify the reaction and products.

Other modifications of my invention will 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.

Claims

I CLAIM:

1. The process for the production of poly (polyiso¬ cyanate alkali metal silicate) prepolymer by the following steps:

(a) mixing 1 part by weight of an alklai metal silicate and 0.5 to 6 parts by weight of a polyisocyanate or polyisothiocyanate;

(b) agitating the mixture at 30 to 40 for 10 to 30 minutes, thereby

(c) producing a poly (polyisocyanate alkali metal silicate) prepolymer.

2. The process accoring to Claim 1 wherein the alkali metal silicate has a M₂0:Si0₂ ratio of 1:1 to 1:4 wherein M is an alkali metal.

3. The process according to Claim 1 wherein the polyiso¬ cyanate is selected from the group consisting of arylene polyisocyanates; alkylene polyisocyanates, phosgenation product of aniline-formaldehyde conden¬ sation and mixtures thereof.

4. The process according to Claim 1 wherein the poly¬ isocyanate is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof.

5. The process according to Claim 1 wherein the poly¬ isocyanate is a phosgenation product of aniline-formal¬ dehyde condensation.

6. The process according to Claim 1 wherein a curing agent in the amount of up to 2 parts by weight is admixed with the poly (polyisocyanate alkali metal silicate) following step (c) of Claim 1 thereby producing a poly (polyisocyanate silicate) cellular solid product.

7. The process of Claim 1 wherein from up to 50% by weight, based on the reaction mixture, of a chemical inert blowing agent, boiling within the range of from -25 to 80 C is added after step (c) of Claim 1 then heating the prepolymer to 50° to 80° C while agitating until the chemical reaction begins, thereby producing a poly (polyisocyanate silicate) cellular solid product.

8. The process according to Claim 8 wherein a polyol is admixed with the poly (polyisocyanate alkali metal silicate) prepolymer following step (c) of Claim 1 in the amount of 0.1 to 3 parts by weight thereby producing a poly (urethane silicate) cellular solid product.

9. The process according to Claim 8 wherein the polyol selected from the group consisting of glycerol, gly¬ cerol monochlorohydrin, ethylene glycol, pro- pylene glycol, butylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexa¬ methylene glycol, diethylene glycol, dipropylene glycol, polypropylene glycol, tetraethylene glycol, polyprolyene glycol, tetraethylene glycol, ether glycols, Bis-phenol A, resorcinol, bis (beta- hydroxyethyl) terephthalate, 2-ethyl-2-(hydroxymethyl) -1, 3-propanediol, pentaerythritol, quinitol, mannitol, sorbitol, methyglucoside, glycose, starches, fructose, cane sugar, molasses, dextrines, corn syrup, maple syrup, castor oil, dibutylene glycol, polybutylene glycol, polyester resins with free hydroxyl groups, polybutadienes which contain hydroxyl groups, poly¬ carbonates which contain hydroxyl groups, trimethylol ethane, trimethylol propane, hexane-1,2,6-triol, butane-1,2,4-triol, 1.8-octane-diol, and mixtures thereof.

10. The process of Claim 1 wherein a vinyl monomer is mixe with the poly (polyisocyanate alkali metal silicate) prepolymer following step (c) of Claim 1 in the amount of 0.1 to 3 parts by weight and selected from the grou consisting of acrylonitrile, styrene, methyl styrene, _ vinyl acetate, l,l'-dichloroethylene, n-vinyl-2- pyrrolidone, acrylic acid, methacrylic acid, methyl methacrylate, methacrylonitrile, and mixtures thereof, then heating the mixture to 50° to 80° C

^' while agitating until the chemical reaction begins, thereby producing a poly(urethane silicate) cellular, solid.

11. The process of Claim 1, wherein from up to 10% by weight, based on the reaction mixture of a curing agent and/or catalyst is added following step (c) of Claim 1, thereby producing a poly (polyisocyanate silicate) cellular solid product-

12. The process of Claim 1 wherein from up to 50% by weight, based on the reaction mixture, of a blowing agent, boiling within the range of from -25 to

80 C, is added in step (c) of Claim 1, then the mixture is heated to 50 to 80 C while agitating until the chemical reaction begins, thereby producing a poly (polyisocyanate silicate) cellular solid product.

13. The process of Claim 1, wherein up to 20% by weight, based on the reaction mixture, of an emulsifying agent is added in step (c) of Claim 1.

14. The process of Claim 1 wherein up to 20% by weight, based on the reaction mixture, of a foam stabilizer is added in step (c) of Claim 1.

15. The process of Claim 1, wherein organic or inorganic particulate or pulverulent materials are added to the reaction mixture in the amount of up to 50% by weight, based on the reaction mixture.

16. The product, poly (polyisocyanate alkali metal silicate) prepolymer, as produced by the method of Claim 1.

17. The process of Claim 1 wherein an allyl type halide which has the general formula

H C=C-CH_X t x-

R wherein R is a hydrogen or a C, to C . alkyl group and X is chlorine or bromine and is added in the amount of 0.1 to 2 parts by weight following step (c) of Claim 1. to the poly (polyisocyanate alkali metal silicate) prepolymer, then the mixture is heated to 50° to 80 C while agitating until the chemical reaction begins, thereby producing a poly (poly¬ isocyanate silicate) cellular solid product.

18. The process of Claim 17 wherein the allyl type halide is selected from the group consisting of allyl chloride, allyl bromide, methallychloride, methallyl bromide and mixtures thereof.

19. The product, poly (urethane silicate) cellular solid as produced by the process of Claim 8.

20. The product, poly (urethane silicate) cellular solid, as produced by the process of Claim 10.

21. The product, poly (urethane silicate)cellular soli as produced by the process of Claim 17.

22. The process of Claim 1 wherein 0.1 to 3 parts by weight of a polyol, up to 50% by weight, based on the reaction mixture, of a chemically inert blowin agent, boiling within the range of from -25 to 80 C, up 10% by weight of a curing agent and/or catalyst, percentage based on the weight of the reaction mixture, up to 20% by weight based on the reaction mixture, of an emulsifying agent, up to 2 by weight, based on the reaction mixture, of a foa stabilizer, are mixed with the poly (polyisocyanat alkali metal silicate) prepolymer and allowed to react thereby producing a poly (urethane silicate) cellular solid.

23. The process of Claim 1 wherein the alkali metal silicate is sodium metasilicate pentahydrate.

HTU

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