NL8020181A - - Google Patents

Description

4 N / 30,418-Kp / Pf / vdM

- 1 - 80 2 0 1 8 1! ! i i ΐ! I Preparation of poly (polyisocyanate silicate) solid or cellular | solid using alkali metal silicates.

i: i; The invention relates to a working; way of preparing poly (polyisocyanate alkali metal) -; prepolymer by chemical reaction of a polyisocyanate with an alkali metal silicate by mixing it and then; ; 5 to heat the mixture to obtain a poly (polyisocyanate alkali metal) prepolymer. The poly (polyisocyanate, alkali metal silicate) prepolymer is cured by heat or a curing catalyst such as water. |

The invention relates to a working; 10 method for the preparation of poly (polyisocyanate silicate) solid or cellular solid by reaction of a polyurethane compound with an alkali metal silicate to form a poly (polyisocyanate alkali metal silicate) prepolymer. The prepolymer can be cured by heating or by adding a curing agent. The products prepared by this method may vary widely in physical properties; these can be solid or porous, rigid or elastomer and the porous products can be rigid or soft and flexible.

| ! The products prepared according to the invention can be used as thermal insulation material, sound-proof material, foam material in boats, shock absorbers.

resistant packing material, in the form of cushions, of fiber, of i i '' I

; coating material, of fillers, of impregnating agents,! : of adhesive material, of casting material, of putty and as building elements for a building, etc. The products have improved heat and flame resistant properties. The products are new and economical. Some of the products have some physical properties like wood.

The reaction of alkali metal silicates and mono-alkali metal silicates with polyisocyanates to yield polyurethane siliceous resins and foams are listed in U.S. Patent Application No. 71,628 filed September 11, 1970 by David H. Blount, which is now obsolete.

35; The alkali metal silicates, mono-alkali 8020181 - 2 - j. j! ; | metal silicates and mixtures thereof can be prepared by any of the well-known methods of the art, j A useful mixture containing alkali metal silicate and predominantly mono-alkali metal silicas can be prepared by heating 1-2 moles of an alkali metal hydroxide with about 1 µmol of finely powdered silica in water at a temperature of 80-100 ° C, while operating at ambient pressure for 20-60 min stirred until the water has evaporated. Mono-alkali metal silicate can also be prepared by heating 1 mole of hydra-; 10 silica with 1 mole of the alkali metal hydroxide compound in water until the water has evaporated. It deserves the preference, ! i i '; : that the alkali metal silicate is in the form of a powder.

The poly (polyisocyanate silicate) solid or icellular solid products can be modified or improved by adding organic compounds, inorganic compounds and / or organosilicate compounds. This | bonds can be added before the isocyanate and the alkali metal silicate are reacted with each other or they can be added after a poly (polyisocyanate-120 silicate) prepolymer has been formed. Organic polyols, polyesters, polyether glycols and polysulfides, polybutadiene, butadiene styrene copolymers and butadiene acrylonitrile containing free hydroxyl groups can be used according to the invention. 25: According to United States Patent; 4,072,637 and U.S. Patent Application No. 663,924, filed | | Serving March 4, 1976 by David H. Blount, silicic acids are used to react with polyisocyanates to form poly (polyisocyanate silicate) resins and foams.

All kinds of alkali metal silicate compounds can be used according to the invention, such as sodium,; [potassium and lithium silicates. Other alkali metal silicates i can be used. Sodium silicate and mono-sodium silicate are preferred as alkali metal silicates because they; | be cheap and easily available. The costs are | further reduced by the use of a significant quantity: [1] water as a curing catalyst, which is used in 8020181-3 product. The crude commercial alkali metal silicates may contain other materials, such as calcium silicate, magnesium silicate, aluminates or borates, and are also useful. The mole-; ratio of tfo ^ / SiC ^ (Me = metal) is not critical and can; ! 5 'range from 4: 1 to 0.1: 1.

| Any suitable polyisocyanate can be used according to the invention, e.g. arylene polyisocyanates, such as itolylene; meta-phenylene; 4-chlorophenylene-1,3-; methylene bis (phenylene-4 -) -; biphenylene-4,4'3,31-dimethoxy-bipheny- 10th borrow-4.41-; 3,3'-diphenylbiphenylene-4,4'-; naphthalene-1,5-;

and tetrahydronaphthalene-1,5-diisocyanates and triphenylmethane-1

and trisocyanate, alkylene polyisocyanates, such as ethylene; i, ethylidene; propylene-1,2-; butylene-1,4-; butylene-1,3-; | hexylene-1,6-; decamethylene-1.10-; cyclohexylene-1,2-; cyclo-15hexylene-1,4-; and methylene bis (cyclohexyl-4,4 '-) diisocyanates. Phosgenation products of aniline formaldehyde condensation can be used. Polyisothiocyanates, inorganic polyisothiocyanates, polyisocyanates, containing carbodiimide groups i | contain, as described in German patent 20 1,092,007, and polyisocyanates, which contain urethane, allophanate, isocyanurate, urea, imide or biuret groups, can be used for the preparation of poly (polyisocyanate silicate) ) solid or cellular solid. Mixtures of the above-mentioned polyisocyanates can be used.

In general it is preferred to use commercially available polyisocyanates | such as toluene-2,4- and -2,6-diisocyanate or a mixture of these isomers ("TDI"), ("crude MDI"), polyphenylpolymethylene isocyanates, which are obtained by aniline formaldehyde-30 condensation followed by phosgenation and modified poly | isocyanates, which contain carbodiimide, urethane, allophanate, iso- i contain cyyanurate, urea, imide or biuret groups.

The alkali metal silicate and / or mono-alkali metal silicate can be reacted in an amount of 0.1-2 moles with 1 mole of the polyisocyanate compound j by passing it at a temperature from ambient to 45 ° C, at preferably from 30-40 ° C, while stirring for 10-30 min, yielding yellow granules of 8 0 2 0 1 8 1 - 4 - a poly (polyisocyanate alkali metal silicate) prepolymer. It ; The prepolymer can be cured by heating above 50 ° C or! by adding a curing agent such as water and a solid or cellular solid product.

: 5 All kinds of polyols can be added to the alkali metal silicate before the polyisocyanate becomes | added or after the poly (polyisocyanate alkali silicate) ivory polymer has been formed. Poly- lols include, for example, glycerol, glycerol monochlorohydrin, ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, itetraethylene glycol, polyethylene glycol; ether glycols, bisferol A, resorcinol, bis (beta-hydroxyethyl) -! jl5 terephthalate, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, penta-1 | erythritol, trimethol propane, trimethol ethane, 2,2-osydiethane! ; nol, quinitol, mannitol, sorbitol, methylglucoside, glucose, starches, trimethylolethane, trimethylolpropane, hexane-1,2,6-: triol, butane-1,2,4-triol, 1,8-octanediol, fructose, cane: 20 sugar, molasses, dextrins, corn syrup, maple syrup, castor | oil, dibutylene glycol, polybutylene glycol, polyester resins with free hydroxyl groups, polycarbonates with hydroxyl groups 1! and mixtures thereof.

All kinds of polyesters containing free hydroxyl or ii; 125 containing icarboxyl-terminal groups can be used .;

Lactone polyesters, such as ε-caprolactone, 1 'polyesters! hydroxycarboxylic acids, such as hydroxycaproic acid, can be used. The hydroxy groups containing polyesters can be; prepared by reacting polyhydric alcohols, preferably 30 dihydric alcohols with optional addition of trihydric alcohols, with polybasic carboxylic acids, of which the dibasic carboxylic acids are preferred. The corresponding! polycarboxylic anhydrides or corresponding polycarboxylic acid esters, of lower alcohols or mixtures thereof, can be used to prepare the polyesters instead of; or in combination with the free polycarboxylic acids. The polycarbonate; acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and can be substituted, e.g. with 8 02 0 1 8 1 - 5 -

; I I

halogen atoms and may be unsaturated. Suitable compounds are adipic acid, azaleic acid, succinic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, imaleic acid, fumaric acid, dimer and trimer fatty acids (such as 5 oleic acid mixed with monomeric anhydride, tetrahydrophthalohydride anhydride endomethylene tetrahydrophthalic acid; anhydride, maleic anhydride, glutaric anhydride, bis-glycol terephthalate, dimethyl terephthalate and mixtures thereof and can be reacted with the listed polyols, to yield a polyester which can be used according to the invention. The preparation of polyesters is known in the prior art. j

The polyesters having 2-9 hydroxyl groups can be prepared by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, each by itself or by adding these epoxides or mixtures thereof with alcohols I; or amines. Polyethers can be modified with vinyl-20 polymers, such as styrene or acrylonitrile. i I Various polyacetals, polythioethers,! | polyesteramides, polyamides, polyhydroxyl compounds already containing urethane or urea groups, modified or | unmodified natural polyols, addition products of alkylene oxides with phenol formaldehyde resins or with urea formaldehyde resins are used according to the invention and are used; added to the alkali metal silicates or after the poly; (polyisocyanate alkali metal silicate) prepolymer is formed. These polymers can be added in an amount of 0-100 wt. % based on the weight of polyisocyanate.

Examples of the compounds to be used according to the invention are described in e.g. High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", published by Saunders-Frisch, Interscience Publishers, New; : 35 York, London. Also in Vol. I, 1962, pp. 32-42 and pp. 44-54 and in Vol. II, 1964, pp. 5-6 and pp. 198-199.

A preferred embodiment of the work; The method according to the invention for the preparation of poly (poly-8020181-6-isocyanate silicate) solid or cellular solid products consists of mixing about 1 part by weight. of a finely powdered alkali metal silicate with 0.5-6 parts by weight. of a polyisocyanate or polyisothiocyanate. The mixture should then be heated; 5 to 30-40 ° C with stirring at ambient pressure and for; ! 10-30 minutes to form yellow granules of poly (polyisocyanate alkali metal silicate) prepolymer. Then, | If desired, the prepolymer is heated to 50-80 ° C, while stirring at ambient pressure, and immediately begins to expand to about 3-12 times its original volume, forming a rigid, standing poly ( polyisocyanate silicate) cellular solid. !

Instead of heating, a curing agent can be added to the poly (polyisocyanate alkali metal silicate) pre-Il5 polymer in an amount of 0.001-10 | wt% based on the reagents. The curing agent is mixed thoroughly with the prepolymer and rapidly expanded to 3-12 times its original volume to form a rigid, standing poly (polyisocyanate silicate) cellular. Solid.

| According to another method, about 1 part by weight. of a finely powdered alkali metal silicate and 0.5-6 parts by weight. of a polyisocyanate and then heated under stirring at ambient pressure to 50-80 ° C. The mixture begins to expand when the temperature has reached 50-80 ° C ! reaches and expands to 3-12 times the original volume ,; To form a rigid, standing poly (polyisocyanate silicate) cellular solid product.

In yet another method, a curing agent is added to the mixture of alkali metal silicate and polyisocyanate. The mixture is then stirred at ambient pressure. In a few minutes (1-15 min) the mixture expands to 3-12 times its original volume, by molding a poly (polyisocyanate silicate) cellular solid, or is cured to a solid product.

| Polyols in an amount of 0.1-3% by weight; | parts. can be chemically reacted with 1.5-7 parts by weight. poly (polyisocyanate alkali metal silicate) prepolymer ,; 802018t-7-i i to form poly (urethane silicate) solid or cellular; 1 | solid products. The polyols can also be used simultaneously; iden mixed with the alkali metal silicate and polyisocyanate, ion formation of poly (urethane silicate) solid or cellular solid products.

Any of the suitable vinyl monomers can be chemically reacted with the poly (polyisocyanate: sodium alkali metal silicate) prepolymer, the mixture of alkali metal; metal silicate and polyisocyanate, alkali metal silicate, the J10 mixture of the listed organic compounds and polyiso- | Icyanate or the mixture of alkali metal silicate, polyol and polyisocyanate to form poly (urethane silicate) solid | praise cellular solid products. j

Several suitable vinyl monomers can be used 15 s are used, eg, acrylonitrile, vinyl acetate, isyrene, methyl styrene, 1,1'-dichloroethene, n-vinyl-2-pyrolylidene, vinyl toluene, n-vinyl carbazone, 2-vinyl pyridine, 4-! vinyl pyridine, 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, | crotonic acid, chloroacrylic acid, fluoroacrylic acid, cyclohexyl- | | imethacrylic acid, isobutyl methacrylic acid, bromoacrylic acid, benzyl; | lacrylic acid, methyl methacrylate, propyl acrylate, butyl acrylic acid,! | ipropyl acrylate, butyl acrylate, pentadecylacrylate, hexadecyl acrylate, benzyl acrylate, cyclohexyl acrylate, phenylethylacrylate, ethyl methacrylate, methyl alpha-chloroacrylate, 2-chloro-ethyl acrylate, 1,1-dihydro-acrylate-lauryl butyl acrylate late, cyclohexylcyclohexyl methacrylate, allyl methacrylate, | ethylene methacrylate, n-butyl methacrylate, polyethylene glycol; 30 dimethacrylate, tetraethylene glycol dimethacrylate and mixtures thereof. The vinyl monomers are added in an amount of 0.1-3 parts by weight. per 0.5-6 parts by weight. of the polyiso-I cyanate.

| ; All kinds of suitable halides of the allyl type can be chemically reacted with the: poly (polyisocyanate alkali metal silicate) prepolymer, a | mixture of alkali metal silicate and polyisocyanate or one; mixture of alkali metal silicate, polyol and polyisocyanate, 8020181-8-8 to form poly (urethane silicate) solid or cellular solid products.

Such suitable allyl-type halides have the general formula: I ^ C = C 1 -R 3 -Ci ^ X, wherein; R is a hydrogen atom or a C 1 -C 6 alkyl group and X is chlorine or! is bromine. |

As representative examples of such halides of the allyl type, mention is made of allyl chloride, allyl bromide, crotyl chloride, crotyl iodide, beta-methylallyl chloride, beta-methylallyl bromide, methylvinylcarbinylchloride, methylvinylcarbinylfluoride, alpha-dimethylallyl!

S i · I

chloride / beta-cyclohexylallyl chloride / cinnamyl chloride, | beta-ethylcrotyl chloride, beta-phenylallyl bromide, alpha-dicyclo- hexylallyl chloride, beta-propylallyl iodide, beta-phenylallyl-i

Chloride, beta-cyclohexylallyl fluoride, 2-chloromethylbutene, 1,2-chloromethylpentene-1,2-chloromethylhexene-1 and mixtures thereof.

Plasticizers, fillers, cure rate modifiers, pigments, extenders and the like can be added to the blends of the invention or can be added to the prepolymers during curing and the amount can be from 5-50 wt% , yes

Based on the weight of the prepolymer or mixture. If | Plasticizers are suitable benzodate esters, dipropylene glycol benzoate, dodecyl phthalate and propylene glycol phthalate. Suitable i i; | Cutting agents are high boiling coal tar distillates, mineral oil, poly (alpha-methylstyrene) polymers, liquid polysulfide polymers with mercapto end groups, paraffin oil and sulfonated castor oil. Finely powdered filler; 30 parts, such as alkali metal silicates, ammonium silicate, metal oxides, metal hydroxides, metal carbonates, lime, heavy spar,! . Igips, anhydrite and mixtures thereof can be used according to the present invention. j

When preparing certain foams! : i | It is recommended to add blowing agents. These are liquids with a boiling point in a range of -25-80 ° C, at;

O

Preferred -15-40 C. The organic blowing agents are used in amounts of 2-30% by weight, based on the reaction mixture. 1:; j isel. The organic blowing agents, such as acetone, ethyl acetate, [halogenated alkanes, eg methylene chloride, chloroform, ethylene chloride, vinylidene chloride, monofluorotrichlorine | methane, chlorodifluoromethane, dichlorodifluoromethane, and also>; Butane, hexane, heptane, diethyl ether, and compounds which decompose at temperatures above room temperature with gas release, such as nitrogen, eg azo compounds and azo isobutyric nitrile, can be used in this method. Finely divided metal powders, e.g., calcium, zinc, magnesium il0 and aluminum, can serve as blowing agents by releasing hydrogen in an alkaline solution. Other curing agents or catalysts in combination with water or instead of water can be used as catalyst for the j; Forming foams from the poly (polyisocyanate alkali metal silicate) prepolymers and the mixtures of alkali metal silicate and polyisocyanate. These catalysts are well known in the art and include, for example, tertiary amines, silo amines, basic compounds which contain nitrogen.

Containers such as tetraalkylammonium hydroxide, alkali metal pheno [20], alkali metal alcoholates, hexahydrotriazines, tin organo [metal compounds and mixtures thereof. These catalysts are generally used in an amount of 0.001-10

| [wt%, based on the weight of the reaction mixture. I

As foam stabilizers, mainly water-soluble polyether siloxanes and those which are used are suitable.

disclosed in U.S. Pat. No. 3,629,308. j! : I

i These additives are preferably used in amounts j [of Q-20 wt%, based on the reaction mixture. j

Other examples of surfactant I.

30 [additives, foam stabilizers, cell regulators, negative catalysts, stabilizers, flame retardants, plasticizers1, dyes, fillers and fungicides or bacteriocides; and details of methods of using these [additives and their action can be found in: i ' j 35 [Kunststoff-Handbuch, Vol. VI, published by Vieweg and | Hcchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 103-113.

; The quantitative ratios of the reagent üko?: Ïlc βΌ 2 0 18 1 - 10 - i J! The materials used according to the invention are not critical and accurate measurements are not necessary. The amount of each of the reagents can vary. In the preparation of poly (polyisocyanate silicate) solid or cellular solid product and poly (polyisocyanate organosilicate) solid or cellular solid products, a thick liquid or soft solid prepolymer can be formed when an excess of alkali metal silicate and an organic compound are used. The prepolymer can then be reacted with the polyisocyanate to form a solid or cellular solid product. The soft solid prepolymer can! j are used as putty, for surface coatings, or j adhesives, species composition and for preparation of foams. It can also be machined by injection molding,! 15 extrusion or in a kneader.

When to use the solid or cellular solid product prepared according to the invention | Under conditions where high temperature resistance and | a complete flame resistance is necessary, it is prepared by applying a silicate content of 70-95% and | using a non-volatile curing agent such as mineral acids, hydrogen-containing salts, ammonium salts, etc. j Compressed air can be used as a blowing agent. Flame retardant | agents such as halogenated paraffins and inorganic salts 25 or phosphoric acid can be added.

| The methods of the invention can are performed in the readily available mechanical; instruments. The cellular solid products can be obtained by mixing the reagents in one or more steps in a continuous or intermittent mixer. The mixture of reagents will expand to yield the cellular solids products outside the agitator. If desired, the prepolymer can be prepared in advance and prepared! ! . j are then expanded by heat, a curing catalyst, 1 i 1! A blowing agent or by adding more polyisocyanate.

The prepolymers of the invention are cured by heating at a temperature of 50-200 ° C. Once initiated, the hardening reaction is generally none

0i * 02? LC

8020181 - 11 - external heat more needed to complete the hardening process.

If the desired degree of foaming is not achieved, hollow expanded granules of glass or plastic or hollow natural materials can be used to form cellular solid products. The products of the invention can be formed as cellular. Solid grains by dripping the hardening mixtures in petroleum hydrocarbons or by free fall. These grains 10 can be compressed or mixed with other light ones; or expanded materials, including expanded glass, expanded clay, wood, cork, popcorn, hollow plastic granules, eg | travel of polystyrene, polyethylene, polypropylene, polyvinyl- [chloride, polysulfone, polyepoxide, polyurethane, urea formal-; [Dehyde, phenol formaldehyde or polyimide and are added to mixtures according to the invention before curing. The cured product can be used as an insulating material with good fire resistance properties, as construction elements in the construction industry, furniture industry and motor vehicle or aircraft industry. The granules of the cellular solid product in crumbly form can be used for soil [improvement.

; [The expanded mixtures of the invention [can be sprayed on walls, earthen embankments, fabric |, [chicken wire, fiberglass sheeting and fibers, walls or caves, mines, tunnels, etc., to form a cellular solid layer for insulation and protection. The expanded mixtures [[can be used for sealing joints, for sealing [and sealing surfaces, for setting up! j30! walls and houses, for printing, insulating and decorating, for [cladding as living material, as adhesives, mortars, I, i [casting compositions and fillers. The foams can harden • and drying on the surface on which they are sprayed.

The expanded mixtures of the invention! i 35 can in many cases be molded and used in place of wood. The cured products can be; | sawn, nailed, drilled, flattened, milled and treated like wood. The mixtures can be 1 8 0 2 0 1 8 1 - 12 -! ! ; I: Ns are extruded through spinnerets and slots to form fibers or thin sheets and can be used in the manufacture of paper or as a filler in papermaking, etc.

All kinds of fillers can be added to the mixture according to the invention in considerable amounts without losing the favorable properties. Fillers in the form of fine particles or powders are preferred, such as lime, dolomite, gypsum, glass, carbon, etc. Lanhydrite and the usual plastics. Other fillers in the form of granulates, threads, fibers, crystallites, rods, coils, grains, foam particles, woven or knitted fabrics, tapes, foil, fillers or solid inorganic or; inorganic substances, such as sand, alumina, asbestos, aluminum; oxide and hydroxide, zeolites, calcium sulfates, aluminum silicates, cements, basalt powder or wood, glass fibers, carbon fibers, graphite black, Al, Fe, Cu and Ag powders, steel wool, bronze or copper mesh, silicon powder, glass powder, wood chips ,; sawdust, lignin, cork, cotton, straw, popcorn, coke or particles filled or unfilled, foamed or non-foamed, stretched: 20 or unstretched organic polymer can be used. Such organic polymers are polystyrene, polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polyisoprene. i: | | polytetrafluoroethylene, aliphatic and aromatic polyesters, | ! imelamine urea resins, polyacetal resins, polyethers, polyether; i I! Isilicate polymers, polyureas, polyepoxides, polyhydantoins, polysulfones, polyurethanes, polyimides, polyamides, poly-carbonates and any copolymer thereof. i

The object of the present invention is to provide a new process for the preparation of poly (polyisocyanate silicate) solid or cellular solids.

"I

products. A further object is the preparation of new poly (urethane silicate) solid or cellular solid products.

Another aim is to prepare relatively inexpensive products foamed and elastomeric inorganic-organic plastics. Ver-; Another object is the preparation of new cellular solid products which are relatively inexpensive, rigid, fine cellular, lightweight and very strong and exhibit good flame resistance and dimensional stability upon heating.

oleine 8020181 - 13 - i: In addition, another object is the preparation of inorganic-organic plastics, which can be used for thermal insulation, construction purposes, soundproofing, shock-resistant packaging, cushions, wood and metal cladding, adhesives , casting material, putty, etc.

! The invention is now further illustrated by the following examples, which preferred embodiments illustrate, but not limit, the procedures that may be used in; the preparation of poly (polyisocyanate silicate) solid or cellular solid products. Parts by weight and percentages' | unless otherwise specified.

EXAMPLE I

Approx. 1 part by weight. granular sodium metasilicate pentahydrate and 1 part by weight. toluene diisocyanate (80%, 2,4-domer and 20% 2,6-isomer) were mixed and then heated to 30-40 ° C with stirring for 10-30 min, forming a mixture of poly (toluene diisocyanate sodium). [silicate) prepolymer, sodium silicate and toluene diisocyanate. The mixture was then heated to about 50 ° C, leaving it; | mixture rapidly expanded to 3-12 times the original volume [[me, to form a rigid, upright poly (toluene diisilic cyanate silicate) cellular solid.

i! j! EXAMPLE II j 25 | Approx. 2 parts by weight. granular potassium metasilicate pentahydrate and 3 parts by weight. Toluene diisocyanate were mixed and then heated to 30-40 ° C with stirring at ambient pressure for 10-30 min. using a mixture of poly (toluene diisocyanate potassium silicate) prepolymer, toluene diiso-; Cyanate and potassium silicate were formed. 1! The mixture was then heated to approx.

50 ° C while still stirring, the mixture rapidly expanding to 3-12 times the original volume, forming a rigid upright poly (polyisocyanate silicate) -cellular solid.

| EXAMPLE III

Dry powdered hydrated silica j was heated together with sodium hydroxide in a 1: 1 molar

Ot-10 / LC

8020181 - 14 -

I I

In an aqueous solution until the water had evaporated to form granules of sodium silicate and monosodium silicate. Approx. 2 parts by weight. of this mixture of granules and 2 parts by weight. toluene diisocyanate was mixed and then heated to 30-40 ° C while stirring at ambient temperature. : atmospheric pressure, after which yellow granules of poly (toluene diisocyanate, sodium silicate) prepolymer were formed. Then it became; prepolymer heated to about 50 ° C with continued stirring, 1 ii; and rapidly expanded the mixture to 3-12 times its original volume, forming a rigid, upright poly (toluene diisocyanate silicate) cellular solid dust product. |

EXAMPLE IV

-! I Approx. 1 part by weight. finely powdered silica and 1 y! : parts sodium hydroxide were mixed in water and then! j: 15 heated to 80-100 ° C until the water had evaporated / after which a white powder was obtained which is essentially monosodium: | silicate and sodium silicate.

; Approx. 2 parts by weight. of the white powder and 3 y parts by weight. toluene diisocyanate (80% 2.4 isomer and 20% 2.6-20 isomer) were mixed and then stirred for

j Q

| Heated 10-30 min to 30-40 ° C to form poly (toluene diisocyanate sodium silicate) prepolymer. The prepolymer j [was then heated to above 50 ° C with continued stirring the mixture rapidly expanding to 3-12 times the original volume, forming a rigid, upright poly-: | .: (toluene diisocyanate silicate) cellular product. j

EXAMPLE V

, About equal parts by weight finely powdered! 1/3 silica and sodium hydroxide chips were mixed in 30 µl water then stirred for 20-60 min at ambient temperature:

Boiling pressure heated to 80-100 ° C until the water had evaporated ,; whereby a white powdered mixture of sodium silicate and mono-sodium silicate was formed. Approx. 1 part by weight. of the granular mixture of sodium silicate and mono-sodium silicate 35 and 2 parts by weight. toluene diisocyanate (80% 2,4 isomer and 20% 2,6 isomer) were mixed and then heated to above 50 ° C with stirring, the mixture rapidly expanding to | ; 3 -12 times the original volume, forming an i 8020181 - 15 -! rigid, upright poly (polyisocyanate silicate) cellular solid product. j

In the following examples, VI-XVII, 2 parts by weight of the mixture of poly (toluene, 5-diisocyanate sodium silicate) prepolymer, sodium silicate and toluene diisocyanate, as formed according to Example V, were mixed with 1 part by weight of the following reagents. The j mixture rapidly expanded to 3-12 times the initial j! volume, forming a poly (urethane silicate) - j! - 10: product. A curing catalyst in an amount of 0.1-1 | parts by weight can be added together with the organic! reagent.

| TABLE A

I I 1

In front of- ; jl5 image reagent curing agent nature of the product VI n-vinyl-2 - 0.5 part / water rigid cellular solid; | ; pyrrolidone ij ':! VII 1,1-dichloro-0.5 part / water rigid cellular solid; ethylene and 0.25 part /; 20 / ethylenediamine VIII methylstyrene 1 part / water solid! i IX methacryloni- no rigid cellular solid · i vibrate! :! X ethyl acrylic acid no rigid cellular solid; 1 - i 25 1 XI vinyl acetate no rigid cellular solid! XII acrylic acid no rigid cellular solid XIII methyl methacryl solids 1 part / water j; i: XIV allyl chloride 0.5 part / water rigid cellular solid! 30s; XV acrylonitrile 0.5 part / water rigid cellular solid XVI methallylchlo- 0.5 part / water rigid cellular solid! ride. X.V.Ï.I. . ". me.thacry 1 acid. .0.,. 5. share / water! . . . "stig f. cellular, solid

; ----- _J

The following examples XVIII-XXVII, 35 used 1 part by weight of a polyol and '; the mixture of poly (toluene diisocyanate potassium silicate) prepolymer, potassium silicate and toluene diisocyanate as formed! according to example II. These mixtures were mixed with 0-1 8 02 0 1 8 f!

OK025LC

16-part by weight of a curing catalyst, after which a rapid chemical reaction of the mixture occurred, producing a poly (urethane silicate) solid or cellular solid product. Two parts by weight of the mixture of poly (toluene di-5: isocyanate potassium silicate) prepolymer, potassium silicate and di-

isocyanate were used. The results are reported in I.

! table B.

! TABLE B! :; pre-curing example polyolsilicate catalyst nature of product I XVIII glycerol no rigid cellular solid! XIX ethylene glycol no rigid cellular solid XX dipropylene glycol no rigid cellular solid XXI polyethylene glycol no rigid cellular solid 15: (MW 1000); i XXII triethylene glycol no rigid cellular solid! iXXIII polypropylene- no rigid cellular solid i glycol (mol wt.

| 400)! 20 XXIV propylene glycol no rigid cellular solid - XXV polypropylene- no rigid cellular solid! glycol (mol wt.) j! j 320) | | J XXVI mannitol no rigid cellular solid 25 IXXVII castor oil 0.5 part / solid J water! I _; _;

In the following examples, XXVIII-XXXVI,; 2 parts by weight of the mixture of ipoly (toluene diisocyanate sodium silicate) prepolymer, sodium! 30 'silicate and toluene diisocyanate, as formed in accordance with prec Figure I, together with 1 part by weight of a reagent and 1 part by weight of a polyol. The ingredients were mixed each time and the mixture rapidly expanded to 3-12 times the original volume to form a poly (urethane-silicate) product. The results are reported in Table C.

8020181 i j - 17 - TABLE C i: front | ; image reagent polyol nature of the product XXXXl methallylchlo- 2,2'-oxydiethastiff cellular solid i ride nitol XXIX allyl chloride glycerol rigid cellular solid XXX 1,1'-dichloro-1,4-butanediol liquid ethylene XXXI vinyl acetate glycerol rigid cellular solid! 10 XXXII chlorostyrene propylene glycol rigid cellular solid iXXXIII acrylonitrile ethylene glycol rigid cellular solid XXXIV acrylic acid polyethylene semi-rigid cellular glycol j XXXV methyl methacryriethylene rigid cellular solid! 15.Leave glycol! XXXVI styrene 1,6-hexanediol rigid cellular solid; i: j

In the following examples, XXXVI-L,! each time 2 parts by weight of the poly | ; (toluene diisocyanate sodium silicate) prepolymer, as formed according to example III, 1 part by weight of a vinyl mono-polymer; more and 1 part by weight of a polyol. The ingredients were mixed and the mixture expanded rapidly to 3-12 times

i I

the original volume, to form a poly (urethane silicate) product. The results are reported in Table D. j TABLE D | EXAMPLE vinyl monomer. polyol nature of the product! XXXVI acrylonitrile triethylene rigid cellular solid! Glycol XXXVII methyl styrene diethylene glycol soft solid col; XXXVIII styrene ethylene glycol rigid cellular solid | XXXIX vinyl acetate propylene rigid cellular solid; 35: glycol! j i XL 1,11-dichloro-no soft solid j i ethylene XLI v-vinyl-2- no solid j pyrrolidone 8020181 - 18 - j; TABLE D (cont.) | in front of- ; image vinyl monomer polyol nature of the product XLII n-vinyl-2-glycerol semi-rigid cellular: 5: pyrrolidone solid XLIII acrylic acid polypropylene solid! ! XLIV methacrylic acid 1,4-butanediol rigid cellular solid! I XLV methyl methacryglycerol rigid cellular solid! ! let 1o XLVI methacryloniethylene-rigid cellular solid vibrate glycol XLVII hydroacrylic acid pentaerythritol rigid cellular solid XLVIII isoethylvinyl starch rigid cellular solid ether 15 XLIX ethyl acrylic acid liquid polystiff cellular solid ester resin L n-vinylcarbrimethylol rigid cell rigid cell sole propane i

In the following examples L1-LXII, 2 parts by weight of dry powdered sodium metasilicate, 2 parts by weight of toluene diisocyanate were used each time. hate and 2 parts by weight of an organic reagent and these were added simultaneously with stirring. A rapid reaction occurred to form a thick liquid or soft 25 solid with free hydroxyl and silicic groups. To this !

! solid prepolymers, 1 part by weight of toluene diisocyanate j was added and mixed thoroughly. The mixture expanded quickly! to form a rigid, upright poly (polyisocyanate organosilicate) cellular solid product. The results are reported in Table E. J

TABLE E

parts / add! kind of attached nature of it! toluene diimide reagent the product isocyanate product LI 1,4-butanediol soft solid 1 rigid foam!

Lil methylmethacry- soft solid 1 rigid foam I 1 late: LUI propylene glycol soft solid 1 rigid foam '8020181

0 "'; 0? 2L.C

- 19 -! ; ; ! TABLE E (continued) i j! ..... I 'I ..., .. 11 .1. ......... 1.1 ........... ........ - 'ï parts / toe! added [for example, toluene nature of the image reagent the product isocyanate the product

i _: _ I

| LIV acrylic acid soft solid 1 rigid foam? | | LV acrylonitrile solid 0 granules I LVI styrene rigid foam 0 rigid foam LVII allyl bromide soft solid 1 rigid foam 10 LVIII methylstyrene soft solid 1 rigid foam; i LIX methallyl bromide soft solid 1 rigid foam LX glycerol soft solid 1 rigid foam; LXI allyl chloride soft solid 1 rigid skew i LXII methallylchlo soft solid 1 rigid foam1 15 ride j i. . . . !

In the following examples LXIII-LXXXI, i | ; 1 weight part of the j! poly (toluene diisocyanate sodium silicate) prepolymer, as used; [formed in Example IV, which was mixed with 1 part by weight; 20 of a reagent and 0-2 parts by weight of a curing agent, ij: -1j to form a poly (urethane silicate) solid or cellulose | lair solid product. The results are reported in | table F.

! TABLE F |

i - -. . ______ I

25! pre-curing! image reagent medium nature of the product! LXIII glycerol no rigid cellular solid; ! i! LXIV ethylene glycol no rigid cellular solid LXV diethylene glycol no rigid cellular solid LXVI triethylene glycol no rigid cellular solid; LXVII polyethylene glycol no semi-rigid cellular solid: LXVIII propylene glycol no rigid cellular solid LXIX castor oil 0.5 part / semi-rigid cellular 35! water solid LXX polyethylene glycol 0.5 part / rigid cellular solid water 8020181

0K072LC

- 20 - TABLE F (cont'd) | pre-curing | image reagent medium nature of the product LXXI polypropylene glycol not semi-rigid cellular; : 5 i fixed! ; LXXII trimethylol ethane + 1 part / water I; LXXIII castor oil no semi-rigid cellular solid, LXXIV glyptal resin no rigid cellular solid; LXXV 1,6-hexanediol no rigid cellular solid LXXVI adipic acid no rigid cellular solid LXXVII maleic acid no rigid cellular solid LXXVIII phthalic anhydride no rigid cellular solid; 15: LXXIX pentaerythritol no rigid cellular solid. LXXX dibutylene glycol no rigid cellular solid; LXXXI polybutylene glycol 0.5 part / solid j! water! i i I EXAMPLE LXXXII j 20! Three parts by weight of a mixture of an phosphine generation product of aniline formaldehyde condensation product and tolylene diisocyanate with an NCO content of about 30 and 2 parts by weight. powdered sodium metasilicate pentahydrate were mixed and then heated to 30-40 ° C with stirring for 10-30 min to form poly (polyisocyanate sodium silicate) prepolymer. The prepolymer was then | Heated to 50-80 ° C, the mixture expanding to 3-12 times the original volume, forming a rigid upright poly (polyisocyanate silicate) cellular solid.

EXAMPLE LXXXIII i I I i

Three parts. of the liquid crude phosgenation product of an aniline formaldehyde condensate, 2 wt. parts. poly (toluene diisocyanate sodium silicate) prepolymer, 2 parts. sodium water glass (40% ^ 2 * 3: SiO2 = 1: 2), 0.01 35 µg.dl. triethylamine, 0.01 parts by weight. detergent and 1 part by weight. ! Ireland cement were combined and mixed at the same time. The mixture expanded rapidly to 3-12 times the original volume to form a rigid, upright poly- € 020181 -21- (polyisocyanate organosilicate) cellular solid.

The following examples LXXXIV-XCII, i used 3 parts each. toluene diisocyanate, I | 1 part by weight. dry powdered sodium silicate and one of the! ; 5 under listed polyols, the ingredients being simultaneously mixed while stirring at a temperature between ambient temperature and 40 ° C for 10-30 min, to form a poly (urethane silicate) prepolymer. The prepolymer was then heated to 50-80 ° C with continued stirring until the prepolymer began to expand. It expanded to | 3-12 times the original volume to form a poly (urethane silicate) cellular solid. The results ; are listed in Table G.

j I TABLE G yy '' ........ ..........' -— ..............,, '..... ..........., .......... · II I. · i 15 pre-quantity! ; image polyol in parts; LXXXIV glycerol 0.1 y LXXXV propylene glycol 0.2 | LXXXVI polypropylene glycol (400 mol wt.) 2! 20 LXXXVII polyethylene glycol (1500 mol wt.) 3 i! iLXXXVIII castor oil 1.5 i i i LXXXIX liquid polyester resin with free OH-3 j i groups i | XC starch 2 | 25; XCI liquid polybutadiene resin with 2.5 free! OH groups XCII polyether glycol 3: |

Although in the above examples each time specific materials and conditions were mentioned, these only serve to illustrate the preferred embodiments of the invention. Numerous other compositions, apart from the above materials, can be used. The reaction mixtures and products according to the The invention may also contain other agents added thereto in order to improve the reaction and products or 18020181 - 22 - ί ....... Γ .......

1 I I

; i

; ! I

: to be modified otherwise.

Other modifications of the invention will be apparent to those skilled in the art after reading the description

! i caught. These are interventions within the scope of the invention, 1 | 5 as defined in the accompanying claims.

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'! i! I; ; | | i i | 1 'j

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i "i: | i I! | I i! 'i i j: i! : 8020181

Claims (23)

1. Process for the preparation of poly; (polyisocyanate alkali metal silicate) prepolymer by the following steps: 5 a) mixing 1 part by weight of an I alkali metal silicate and 0.5-6 parts by weight. of a polyisocyanate; or polyisothiocyanate; j b) stirring the mixing for 10-30 min; sel at 30-40 ° C, making JlO! c) a poly (polyisocyanate alkali metal silicate) prepolymer is formed. Method according to claim 1, with! characterized in that the alkali metal silicate has a 1 M 2 O: SiO 2 ratio of 1: 1 to 1: 4, M being a; 15! alkali metal. A method according to claim 1, with; characterized in that as a polyisocyanate an arylene polyisocyanate, an alkylene polyisocyanate, a phosgenation; product of aniline formaldehyde condensation or a mixture thereof is used. j Method according to claim 1, with! ; . I; It is characterized in that the polyisocyanate is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate or a mixture thereof. A method according to claim 1, with; 25. characterized in that the polyisocyanate is a phosphogenation product of aniline formaldehyde condensation. 6. Process according to claim 1, characterized in that a curing agent in an amount of up to 2 parts by weight. is admixed with the poly (polyisocyanate alkali metal silicate) following step c) of claim 1 to form a poly (polyisocyanate silicate) cellular; Ivaste fabric product. A method according to claim 1, with; characterized in that up to 50% by weight, based on the reaction mixture, of a chemically inert blowing agent having a boiling point in the range of -25 to + 80 ° C is added after the completion of step c) of claim 1, and then stirring the prepolymer with heating to 50-80 ° C until chemical 8020181 - 24 -! : ί I:; reaction deployment, resulting in a poly (polyisocyanate silicate)! cellular solid product is formed. 8. Process according to claim 1, characterized in that a polyol is admixed with j 5, the poly (polyisocyanate alkali metal silicate) prepolymer, after | i,! the completion of step c) of claim 1 in an amount of 0.1-3 parts by weight, whereby a poly (urethane silicate) cellular solid product is formed. 9. Process according to claim 8, characterized in that as polyol glycerol, glycerol, monochlorohydrin, ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, dipropylene glycol, polypropylene glycol , tetraethylene glycol, polypropylene glycol, tetraethylene glycol, ether glycols, bis- | phenol A, resorcinol, bis (beta-hydroxyethyl) terephthalate, 1,2-ethyl-2- (hydroxymethyl-1,3-propanediol, pentaerythritol, quinitol, mannitol, sorbitol, methyl glucoside, glycose, starch , fructose, cane sugar, molasses, dextrins, corn syrup, 20 maple syrup, castor oil, dibutylene glycol, polybutylene ji, .1 glycol, polyester resins with free hydroxyl groups, polybutanes with hydroxyl groups, polycarbonates with hydroxyl groups, trimethylol ethane, trimethylol propane 1,2,6-triol, ibutane-1,2,4-triol, 1,8-octane diol or mixtures thereof: 25 are used. The method of claim 1, with I. ! ! characterized in that a vinyl monomer is mixed with the poly (polyisocyanate alkali metal silicate) prepolymer following step c) of claim 1 in an amount of 0.1-3-3 parts by weight, the vinyl polymer being selected from the group of acrylonitrile, styrene, methylstyrene, vinyl acetate,; 1,1 * -dichloroethylene, n-vinyl-2-pyrrolidone, acrylic acid, methacrylic acid, methyl methacrylate, methacrylonitrile and mixtures thereof, and then the mixture is heated to 50-35 ° C with stirring until the chemical reaction begins to form a poly (urethane silicate) cellular solid. 11. Method according to claim 1, characterized in that up to 10% by weight, based on 80%. 018 1 0M0 LC * - 25 - the reaction mixture, of a curing agent and / or catalyst; . i is added after step c) of claim 1 to form a poly (polyisocyanate silicate) cellular solid product. i 12. Method according to claim 1, with | The characteristic is that up to 50% by weight, based on J | the reaction mixture, of a blowing agent with a boiling point in in the range of -25 to + 80 ° C, is added during step ic) of claim 1 and the mixture is stirred thereon | heated to 50-80 ° C until chemical reaction sets in to form a poly (polyisocyanate silicate) cellular solid product. ! 13. A method according to claim 1, characterized in that up to 20% by weight, based on | the reaction mixture, of an emulsifying agent, is added 15 'during step c) of claim 1. j The method of claim 1, with | characterized in that up to 20% by weight, based on the reaction mixture, of a foam stabilizer is added! added during step c) of claim 1. i | 20 1 15. Process according to claim 1, characterized in that organic or inorganic | ! Granular or powdery materials are added to the reaction mixture in an amount of up to 50% by weight based on the weight of the reaction mixture. on the reaction mixture. 16. The product, poly (polyisocyanate alkali metal silicate) prepolymer, obtained by the method of claim 1. 17. Process according to claim 1, characterized in that a halide of the allyl type! 30: of the general formula H 2 C = C (-R) -CH 2 X, wherein R is a hydrogen atom or a C 1 -C 6 alkyl group and X is chlorine or bromine, i is added in an amount of 0.1- 2 parts by weight. next; to step c) of claim 1 on the poly (polyisocyanate alkali metal silicate) prepolymer, and then the mixture is heated to 50-80 ° C with stirring, until the chemical reaction begins to form a poly (polyisocyanate silicate) j, cellular solid product. 18. Process according to claim 17, comprising: 92.7L0 8020181 * - 26 - characterized in that as halide of the allyl type allyl chloride, allyl bromide, methallyl chloride, methallyl; bromide or mixtures thereof are used. ; i 19. The product, poly (urethane silicate) -5 cellular solid, obtained using the working; manner according to claim 8. j 20. The product, poly (urethane silicate) cellular solid, obtained by using the working:; I mode according to claim 10. 21. The product, poly (urethane silicate) - cellular solid, obtained using the method of claim 17. 22. Process according to claim 1, characterized in that 0.1-3 parts by weight. of a polyol, from 15 to 50% by weight, based on the reaction mixture, of one µg chemically inert blowing agent, with a boiling point in the range of! i i o! -25 to +80 C, up to 10% by weight of a curing agent and / or catalyst based on the weight of the reaction mixture, up to 20% by weight, based on the reaction mixture, of one! emulsifier, up to 20% by weight, based on the reaction mixture, of a foam stabilizer, are mixed with it; poly (polyisocyanate alkali metal silicate) prepolymer and up to j! ! The reaction is effected to form a poly (urethane, silicate) cellular solid. j; : i! 25 ; A method according to claim 1, characterized in that the alkali metal silicate contains sodium; metasilicate pentahydrate. ! | | I I 30; | i! ; 8020181