IE40271B1 - Inorganic-organic plastics - Google Patents

Abstract

1483270 Organic/inorganic plastics BAYER AG 27 Nov 1974 [30 Nov 1973] 51351/74 Headings C3R and C3P A plastics material is obtained by reaction of (a) 20-85 wt. per cent of an aqueous alkali metal or ammonium silicate solution, (b) 5-70 wt. per cent of an organic isocyanate, and (c) 10-75 wt. per cent of (i) an addition-polymerizable compound and a free-radical initiator or a cross-linking agent, and/or (ii) a phenolic resin, and optionally an acidic hardener, and/or (iii) a urea or melamine resin and optionally an acidic hardener, and/or (iv) an epoxy resin and optionally a polyamine hardener. Preferably at least one of (b) and (c) contains an ionic or hydrophilic group, and these are mixed before (a) is added. In examples a sulphonated crude phosgenated aniline-formaldehyde condensate of reduced dimer content is mixed with an unsaturated polyester/sytrene mixture and benzoyl peroxide (Exaples 1-6), or with a phenolformaldehyde resin part of which is sulphonated (Examples 7 and 8), or with a solution of crude TDI in styrene (Examples 9-18), and optionally CFCl 3 and/or cement, and phenyl diethanolamine; the resulting mixture is mixed with a 44% waterglass solution (Na 2 O : SiO 2 , 1 : 2), which may contain Et 2 N and/or a surfactant. The results are castable or mouldable hard-setting liquids, putties or foams. (From GB1483270 A) [FR2253050A1]

Description

4027 1 It 1m known that polyurelhane plastics and polyurcn plastics nay be produced from polylsocyanates and compounds which contain active hydrogen atoms. Tlie properties of this class of polymer may be widely varied. The high strength, 5 elasticity and wear resistance are considered to be parti cularly valuable properties of these products but their thermostability and, particularly, their dimensional stability at temperatures above 120 'C is only moderate. The use of these products as building and constructional elements is lO limited by their poor fire characteristics. Although these properties may be improved by employing flame retarding agents, in most cases these agents have an adverse effect- on mechanical properties. it is also known to produce organic silica gel plastics 15 by the action of acids or potential acids on aqueous solutions of alkali metal silicates. These plastics have become important particularly as putties and surface coatings. Lightweight foam plastics have also been produced from water glass.

These products have a high dimensional stability to heat and 20 are completely incombustible, but they are brittle and have relatively little strength. However, being foams, they have little ability to withstand loads and crumble under pressure. It would be extremely desirable to combine the advantageous properties of inorganic plastics materials and organic plastics 25 materials while suppressing the negative properties of both.

Accordingly, there has been no lack of attempts to produce combination plastics, but the objective has so far not been achieved.

For example, polyurethanes have been mixed with active 30 silica as a filler and then vulcanized. A certain rein forcing affect Is then observed. The effect is similar to - 2 - 40271 that which Is obtained when using highly active carbon black, that Is to say the tensile strength and modulus Increase but the elongation at break decreases. However, the properties of the material are not fundamentally altered by the addition 5 or silica( presumably because the two components Torn a diphasic system in which only the polyurethane forms a coherent phase while the silica is embedded in the polyurethane as an incoherent phase. The incoherent zones have diameters of the order of from 3 to lOO p. One is therefore dealing with lO relatively coarse heterogeneous diphasic systems. The Interaction between the two phases is only slight, both on account of the relatively small Interface and on account of the very different chemical nature of the two phases.

Attempts have also been made to use silica in a micro-13 fibrous form. The reinforcing effect thereby obtained increases due to the specific morphology of this form of silica,but the incoherent zones inevitably become larger so that the chemical interaction between the two phasoN, if anything, decreases. The fundamental character of a 20 coarse heterogeneous diphasic plastic remains. it 1s also know from British Patent Specification No. 1,186,771 (German Offenlegungsschrift No. 1,770,384), to react an aqueous solution of an alkali metal silicate with a low molecular weight polyisocyanate, e.g. 4,4'-25 diphenylmethane dilsocyanate. In most cases, this reaction results in foams, the lsocyanate phase being caused to react by the presence of water, the carbon dioxide produced causing the mass to foam-up, and some of the carbon dioxide reacting with the surrounding aqueous siiHcate phase which results in 30 gelling of the interface.

The reaction is preferably carried out with the water glass in excess so that the resulting mixture is an emulsion of the lsocyanate in a coherent silicate solution. Therefore, the - 3 - 40271 resulting foam has the character of a silicate foam which contains incoherent zones of foamed polyurea. The properties of such a foam do not differ substantially from those of pure silicate foam. in ract, foams obtained in this way *> are brittle and have little ability to withstand mechanical stress.

Similar effects are obtained with other isocyanates, e.g. cyclohexylisocyanate, phenyllsocyanate, hexamethylene dilsocyanate, diphenylaethane-2,4 '-diisocyanate and tolylene diiso-10 cyanate, as well as adducts of these isocyanates with low molecular weights glycols, e.g. hexane-triol, propylene glycol, hutane-l ,'i-dio], hexane-1,6-diol, neopentyl glycol, glycerol and triraethylolpropane. Although the isocyaimte group-containing organic component which is added to the 13 silicate solution acts as hardener, it has little favourable influence on the properties of the foam and frequently has an adverse effect. The organic component obviously exists mainly as a filler in the finished silicate structure.

An excess of dlisocyanate, on the other hand, results in 20 polyurea foams in which an incoherent silicate phase is dispersed. The properties of these foams are therefore basically those of a polyurea foam which contains silica as filler, and the foams are therefore highly combustible and extremely bri ttle.

If the above-described procedure ,(according to British Patent Specification No. 1,186,771) is adopted in practice, it is found that mixtures of aqueous sodium silicate solutions with diphenylmethane dilsocyanate form only relatively coarse emulsions. Although this disadvantage 30 may largely be overcome by the recommended addition of emulsifiers or foam stabilizers which *-«sult in more Tinely divided and more stable primary emulsions, as a whole, the properties are still unsatisfactory and, in particular, the - 4 - I 40271 combination plastics obtained have a narked brittlenes* and little strength. Prom the results previously obtained it must be concluded that combination plastics of silicates and organic materials have no decisive advantages over wholly ' organic or wholly inorganic materials.

On the contrary, a process has now been found by which macroscopically completely homogeneous inorganic-organic plastics may be obtained which represent solid/solid xerosols similar to the known AliS plastics. The novel composite mat-10 erials obtainable in this way are extremely high quality plastics which exhibit improved properties over wholly organic and wholly inorganic materials. In particular, they are distinguished by their high strength, elasticity, dimensional stability to heat and flame resistance. 15 According to Patent Application No. 2169/73 inorganic-organic plastics characterised by high strength, elasticity, dimensional stability to heat and flame resistance are obtained when liquid prepolymer ionomers, which still contain reactive groups, are sixed homogeneously with aqueous 20 solutions of alkali metal silicates and the resulting sol is left to react to form a xerosol.

The process is particularly suitable for producing inorganic-organic plastics based on isocyanates. Novel, high quality foam concretes based on polyisocyanates, alkali 25 metal silicate solutions and water-binding aggregates are also described in Patent Specification No. 38556.

These foam concretes are particularly important for use as high quality, economical constructional materials which may be used, e.g. in underground and surface engineering 30 and wherever wood has previously been Used.

When carried out in its previous form, the process is subject to certain limitations which may, in certain cases, - 5 - 40271 lie a disadvantage in both technical and economic respects. ^^rbj^Sj jiroiluction.qf .(.hepbove-described inorganic- organic plastics has previously been most successful if polyisocyanates were used as the reactive organic component, *> hut these frequently react so rapidly and completely that the plastic hardens soon after the components have been mixed. This rapid', spontaneous hardening is, in most cases, a great advantage, but it may also lie unties i rahle, p.r. if the material is required to be plastically deformed or il° IO excessive heating of the material lias adverse consequences.

Also, il. would Ite desirable to reduce the cost of the process by employing Inexpensive organic reaclants. l t On the other hand, the cheapest reactive organic resins, e.R. phenol resins, urea resins and unsaturated polyesLer lr> resins, used in combination with alkali metal silicate solutions are less suitable for numerous fields of application because they do not reach their minimum strength sufficiently rapidly to enable them to be subsequently hardened by heat. l-'urthermore they have tin- disadvantage of exerting no direct, influence on 110 silicate hardening.

The above limitations may be overcome by employing mixtures of organic isocyanates and polymerisable and/or polycondensabi c polymer precursors as starting materials and leaving the mixtures to harden in combination with aqueous.alkali metal 25 silicate solutions.

In these combinations, the isocyanate generally acts as the initiating hardening component which causes the organic phase to become viscous or plastic, or even hard; this chanpc is followed by the hardening of the additive component or 30 components. This secondary reaction, (polymerisation and/or polycondensation) may be released simply by the temperature rise produced by the isocyanate reaction or it may be rolease.i - (, - 40371 subsequently by 1 eating.

As will bo ac-cn from the following do*u*r Ipt Ion, a vr*ry wide varloty of fontui I.it loun may l»o iWIik'iI In I lilt) way iu« lli.it practically any raLo and tli'orw i»r hardening may bo achieved. !> Tlio properties of the end products may also be controlled as desired within a wide range.

The present invention therefore relates to a process for producing inorganic-organic plastics which comprises reacting: (a) from 20 to 85%, by weight, based on the total lO mixture, of aqueous alkali metal or ammonium silicate solution; (b) from 5 to 70%, by weight, based on the total mixture, of an organic isocyanate; and (c) from lO to 75% , by weight, based on the total 15 mixture, of (i) polymerisable confounds which contain double bonds, in combination with free-radical initiators or cross-linking agents, and/or (ii) phenol resin condensates and/or precondensates, io optionally in combination with acidic hardeners, and/or (iii) urea resin or melamine resin condensates and/or precondensates, optionally in combination with acidic hardeners, and/or (iv) di- or poly-epoxides, in combination with di-!5 or poly-amines; and (d) optionally, in addition,compounds which are reactive with isocyanates and/or inert aggregates.

Component (c) is preferably selected from: (1) Vinyl monomers and/or unsaturated polymerisable ;0 polyester resins, epoxy ester resins (i.e. resins containing both epoxy groups and ester groups), ester - 7 - 40271 acrylate resins (i.e. containing both ester groups and acrylate groups), ether acrylate resins (i.e. containing both Qther groups and acrylate groups) or urethane acrylate resins (i.b. containing 5 both urethane groups and acrylate groups), all of which contain double bonds, in combination with free-radical initiators or cross-linking agents, (2) Condensates and/or precondensates or mixed condensates and/or precondensates of aldehydes, in particular lO formaldehyde, and phenols, phenol ethers, ureas, or melamines, optionally in combination with acidic hardeners, and (3) epoxy resins.

When the components used according to the present 15 invention are mixed together, liquid to plastic emulsions are formed initially which harden, either spontaneously or when heated, to form colloidal diphexic or multiphasic systems. The inorganic-organic plastics formed in this way are xerosols.

It is particularly preferred to use organic components >o which contain groups capable of interacting with the aqueous inorganic phase. In particular, these are hydrophilic groups. Components which have ionic groups in the presence of the inorganic medium are particularly suitable. The hydrophilic group need not necessarily form a homopolar link with one of the reactive !5 groups of the prepolymer. The presence of at least one group which is capable of interacting with the inorganic phase improves the emulsiflability of the mixture to form a diphasic or multiphasic system with a sufficiently large interfacial area and increases the internal strength of the xerosol. lO According to the present invention, a process in which at least one of the components (b) and/or (c) contains an ionic and/or hydrophilic group - 8 - I 40271 is therefore preferred.

The tern "aqueous alkali metal silicate solution", as used herein, is used to denote the solutions of sodiua and/or , t 1 potassium'silicate in water commonly known as "water glass" 5 although crude commercial solutions which may in addition contain, e.g. calcium silicate, magnesium silicate, borate or aluminates, may also be used. The proportion of Na20 and/or K20;Si02 is not critical and aay vary within the usual liaits, but is preferably from 4:1 to 0.2:1. In cases where the water content 10 of the resulting inorgani<?-organic plastics Is of minor importance, either bemuse it does not interfere or because if may easily be removed by drying, then neutral sodium silicate may well be used, which may be made up into from 2r> to solutions. 15 It is preferred, however, to use Trom 32 to 54£ silicate solutions and these will only have the required low viscosily, (less than 500 poises), necessary for problem-free working-up if they are sufficiently alkaline. Ammonium silicate solutions may also be used but are less advantageous. The "solutions" may 20 be true solutions or colloidal solutions.

The preparation of the inorganic-organic plastics according to the present invention is simple to carry out. All that is necessary is to mix the prepolymer ionomer homogeneously wi th the aqueous alkali metal silicate solution, whereupon, in 25 most cases, the mixture hardens immediately. The mixtures are typical finely divided emulsions or sols. They are not optically clear solutions. In most of the opaque or milky-white emulsions the subsequent xerosol already appears to be preformed. 30 it is preferred to use solutions of sodium silicate which have an Na^OrSiO., molar ratio or from 1:1.6 to 1:3.3.

The isocyanates used according to the present invention may be - 9 - 40271 either ■onoiHocynnales, diisocyanates or polyisocyanates.

Suitable mono 1socyanates Include methyl-, ethyl-, propyl-, butyl-, hexyl-, b-chlorohexyl-, cyclohexyl-, phenyl £-tolyl-, £-nl trophenyl-, j>-methoxyphenyl- and tricliloro-r> phenyl-isocyanate. Those mono isocyanates which contain un additional reactive group are particularly suitable, lor example vinyl isocyanate, isocyanatoethylacrylate, iso-cyanatoethylmethacrylate, isopropenylisocyanate, isopropenyl phenyl isocyanate, methoxymethy 1 isocyanate, m-chloromethyl-11) phenylisocyanate and isocyanatophenylsulphene chloride.

The quantity, or simple monoisocyanates used which do not contain an additional reactive group should not exceed 20%, by weight, based on the total mixture. Their function is that of an initiator Tor the other reaction 15 components.

The organic polyisocyanates used according to tho invention may be aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described e.g. by W. Siefken in .Justus Liebigs Annalan der 20 Chemie, 5<>2, pages 75 to 130, e.g. ethylene di isocyanate, tetrame thylene-1, 'i-di i socyana te, hexamethy 1 ene-1 ,b-di ico-cyanate, dodecane— 1, 12-d i i socyanate, cyclobutane-1,3-diisocyanate, cyclohexane>l.,3- and 1,4-diisocyanat.e and mixtures or these isomers, l-isocyanato-3,3, 5-tri-me thyl-r>-25 isocyanatomethy1-cyclohexane,(see DAS 1,202,785), hexahydro-tolylene-2,*i- and -2,6-di isocyanate and any mixtures of these isomers, hexahydrophenylene-1,3- and/or l,*t-diisocyanate, perhydrodiphenylme thane-2, b and/or bb »-di i socyanate, phenyl ene-1,3- and -1,4-di isocyana t.e, tolylene-30 2,*i— and -2,b-di isocyanate and any mixt ures of ihcsc i somer s di phenyl me thane-2,and/or '-d i isocyanate, naph I by I em— 1,5-di isocyanate, tri phenylmethane-'i, 'i •, V' -1 r i i socyanat o, polyphenyl-polymethylene-polyisocyanates which may be 4 0 271 obtained by nni I Ine—formnldohydcJ condensation roI lowed by phnHftenntion hud which have been described, e.g. In llriLish I'ntent Specification Nos. 874,410 and 848,671, perchlorinated •ryIpolyisocyanates as described'e.g. in German Auslege-schrift No. 1,157,601, polyisocyanates which contain carbodi-imide groups as described, e.g. in German Patent Specification No. 1,0<)'J,007, the diisocyanates described in U.S. PatenL SpeciTication No. "J,492,730, polyisocyanates which contain allophanate groups as described, e.g. in British Patent Speci Tication No. 994,800, lielgian Patent Specification No. 7<>l,b20 and published Dutch Patent Application No. 7,102,524, polyisocyanates which contain isocyanurate groups as described, e.g. in German Patent Specification Nos. 1,022, 780; 1,222,067 and in 1,027,394 and in German Offenlegungsschriften No. 1,020,034 and 2,004,048, polyisocyanates which contain urethane groups as described, e.g. in Belgian Patent Specification No. 752,261 or in U.S. Patent Specification No. 3,394,164, polyisocyanates which contain acylated urea groups according to German Patent Specification No. 1,230,778, polyisocyanates which contain biuret groups as described, e.g. fn German Patent Specification No. 1,101,394, in British Patent Specification No. 889,050 and in French Patent Specification No. 7,017,514, polyisocyanates prepared by a telomerisaLion reaction as mentioned, e.g. in British Patent Specification Nos. 065,474 and 1,072,956, in U.S. Patent Specification No. 3,567,763 and in German Patent Specification No. 1,231,688 and reaction products of the above-mentioned isocyanates with acetals in accordance with German Patent Specification No. 1,072,385.

The distillation residues which are obtained from the commercial production of isocyanates and which still contain lsocyanate groups may also be used, optionally dis 40271 solved in one or more of I lip above-mentl oned polyisocyanates. Mixtures of the above-mentioned polyisocyanates may also be used.

It is generally preferred to use polyisocyanates which 5 are commercially readily available, e.g. tolylene-2,'i- and —2,<»—di isocyanaLe and any mixtures of these isomers, ("TDI"), polyphenyl-polymethylene polyisocyanates which are prepared by aniline-formaldehyde condensation followed by phosgenation, ("crude Mill"), and polyisocyanates which contain carbodiimitle lO groups, urethane groups, allophanate groups, isocyanurate groups and urea groups, ("modified polyisocyanates"), and polyisocyanates which contain imide groups.

It is particularly preferred to use polyisocyanaies which con Lain ionic groups. These ionic groups may have I1) various chemical constitutions. The following arc? mentioned as examples: >n -S-i+\ -I'-W -ax/-), -so,*"), -o-so- ^ K ' (-> ' -i.^4 -i^{") -SO. * ' , -I H 0 "" o 2 ' "^Oll " I'olyisocyunates which contain sulphonic acid and/or sulphonyl ate groups are particularly preferred.

Isocyanates of this type r.iay be prepared by mixinq liquid multi-component mixtures of aromatic polyisocyanates which have an NCO content of from 10 to '<2% by weight, and a -"> viscosity of from 50 to 10,000 el* at 25°C with from 0.1 to 10%, by weight, of sulphur trioxide or an equivalent quantity of oleum, sulphuric acid or chlorosulphonic acid at from -20 to 200°C and leaving the mixture to react and then, il desired, partly or completely neutralizing the resulting sulphonntlon products with a basic compound (see liernan Patent Application No. P ^2 27, 111.0). - 12 - 40271 The known so-called "NCO prepolymers" aay also be used as Isocyanates. Suitable prepolyaers are obtained, for example, by reacting the above-Bentioned Isocyanates with less' than the aolar quantity of aonofunctional, di— 5 functional or polyfunctional compounds which contain /.erewitinof f active hydrogen atoas. Ueactants which are particularly suitable for prepolyaer formation are compounds containing hydroxyl end groups, e.g. polyethers, polyesters, polyether esters, polybutadlenes, butadiene-10 styrene copolymers, polythioethers, polyester aaides, polyacetals, alkyd resins and polyols. The term "prepolyaers" is also used in this context to Include polyisocyanntes which have only been slightly aodified with low aoleculnr weight or higher molecular weight polyols. The NCO pre-15 polymers used aay also be homopolymers or copolymers of unsaturated isocyanates. Crude commercial polyol mixtures are also suitable, e.g. polyols obtained as residues from the production of glycerol, trimethylolethane, trimethylolpropane or dimethylterephthalate. 20 Isocyanate prepolymers which are particularly suitable for producing high temperature resistant plastics are obtained by reacting dilsocyanates or polyisocyanates with subequivalent quantities of diepoxides or dlanhydrides or carboxyanhydrides. Catalysts, e.g. 2,4,6-tris-(dlmethyl-25 aalnomethyl)-phenol, alkali metal salts of carboxylic acids, phenolates, ferrocenes or phospholine oxide or its derivatives are added to the reaction mixture to promote the formation of thermostable isocyanurate or carbodiimlde structures.

NCO prepolymers which may be derived from reeols or 30 amlnoplast condensates and/or precondensates are also particularly suitable. The condensates and/or precondensates are optionally alkaxylatgd.

Particularly suitable NCO prepolymers are those which - 13 - 40271 are also used for preparing polyurethane dispersions, (see Austrian I'ntent Speci ricntion No. li«>7 323), particularly those prepolymers which contain ionic groups or hydrophilic noninnic side chains.

■} Tin* preparation oT ionic N(U> prepolymers which are part i- cularly suitahle for use in the present, process may he carried out in known mnnnrr, Tor example by reacting poly-liydrox.v coiapounds which have a molecular wedght of from 'ton to "JOOO, in part icular polyhydroxypolyes t ers or polyhydroxy-ID polyethers, optionally mixed with polyhydric alcohols which have a molocular weight, below 'i00, with an excess of polyisocyanates, e.g. Iicxatnethy lenedi isocyanate, 2,4-di i socyana t o-toluene, 2,<>—di isocyanateoLoluene or 4,'i '-di isocyanatodi pheny 1-nethane.

I "5 Ionic modification is carried out.,, for example, by adiling a tertiary amino alcohol, e.g. dime thy 1 aminoethanoI or N-methy 1-diethanolamine, and then <|iia tern i y.ing with an alkylating agent. For example, a salt, of an amino acid or of an amino sulplionic acid, may be used for anionic modi I i-20 cation. Carboxydiols, e.g. tartaric acid, dime IhvIo1 propionii-acid or adducts of acid anhydrides and polyols and their sails may also be used for preparing ionic prepolymers. owing i<> the limited storage stability of prepolymers which still contain reactive groups, e.g. hydroxyl groups or free, not ii"> yet. neutralised, carboxyl, urethane or urea groups, it is generally advisable to prepare the prepolymers only shortly before the reaction.

Known prepolymers, particularly those based on aromatic isocyanates, may also b«? subsequently modified lo mnomers', 30 for example by reacting them with sul tones or rt-lac tones <>i by grafLing them, for example with acrylic or me t hacrv I i <: arid or crotonic acid, or by adding sulphuric acid, chlorosu I plumi<• - 14 - 40371 acid, oleua or sulphur trioxide. Excellent prepolyaer lonoaers Tor use according to the invention, which in most cases have a high stability in storage, aay also be obtained'by reacting aromatic Isocyanates, e.g. Lolylene 5 di isocyanates, diphenylaethane di isocyanates and the known phosgenation products of condensation products of aromatic ■onoaaines, such as aniline, and aldehydes, such as formaldehyde, with sulphuric acid, oleua or sulphur trioxlde. Sulphonated polyisocyanates of this type which according U> to tlieir ll( spectrua generally still contain uretdione, urea or biuret groups formed by side reactions during sulplionation and, particularly, also urethane and/or allophanale groups formed by polyol modification before sulphonation ure therefore particularly preferred as prepolymer ionomers. 15 Kven sulphonation of a simple di isocyanate, such as di phenyl me ttmne diisocyanate, in all cases results in a prepolymer ionomer since sulphonation is accompanied by increase in molecular size, e.g. by way of a urea, biuret or uretdione group. 20 It is preferred, however, to use preformed prepolymers for sulphonation, e.g. phosgenation products of higher molecular weight aniline-formaldehyde condensation products which have a viscosity of Trom 50 to 10,000 and preferably from 100 to 5000 centipoises at 25°C. 25 Reaction products of from 50 to 90 mols of aromatic diisocyanates with from 1 to 50 mols of conventional glycols, monoamines, polyether glycols, polythioether glycols or polyester glycols are also particularly advantageous. In these reaction products, the ionic centre may be introduced 30 by adding suitable glycols or by other conventional methods, e.g. subsequent sulphonation or grafting reactions with acrylic acid, malelc acid or crotonic acid or reaction with - 15 - 40271 suit.ones or ('.-lactones.

Kven a very low ionic qroup content is sufficient to ensure the required high compatibility of the prepolymer ionomerM with the aqueous silicate solution, e.g. 2 milliequivalents per lOO y. 5 The amount used is preferably from 5 to lOO milliequivalents per lOO g. In certain cases,'for example if the prepolymer ionomers contain comparatively unreactive isocyanate groups or other end groups, cue amount is approximately 200 milliequivalents per 100 g. The ionic group content may not only constitute salt groups such as 10 the following: -J- <♦>, -i-M. coo<->, ' ' ^ -SO (_), -O-SO (_), -P x (-) ov ' -s02-N(-)-s02", -co-n(_)-c0, -Ar-0(-), lr> but also groups which form salt groups in the presence of alkali metal or ammonium silicate, e.g. -cooh, -so3h, -so2-nh-so2~ -co-nh-co, as well as phenolic OH groups. The prepolymer may, of course, contain two or more of the above-mentioned groups. Prepolymer betaines which contain an anionic and a cationic group in the same molecule or symplexes which contain both anionic and cationic prepolymers • at the same time may also be present.

Tertiary -N-, -COOH-, -SO^i and -AR-OH are particularly preferred groups which form ions. The tertiary amino group must be converted into a quaternary ammonium group before the combination with the alkali metal silicate solution.

This may be carried out with the aid of alkylating agents, or, alternatively, it may be converted to an ammonium group using inorganic or organic acids.

Ionic modification carried out in the conventional manner gives rise to ionomer prepolymers which frequently have a viscosity of more than lOOO cP and occasionally 100,000 cp - 16 - 40271 I or sore at i»5n0. In ciirch where'such high vIhciihIIIch arc a disadvantage in subsequent work ing-up, ihe viscosity nay be lowered by adding low .visCosity isocyanates or inert solvents.' Moreover, the hardening process say be prolonged 5 by combining iononer prepolymers with conventional low viscosity isocyanates.

I'repolymer ionomers which are particularly suitable are prepared by sulphonating aromatic prepolymers. In the simplnsL case, this may he done by reacLing the prepolymers 10 with concentrated sulphuric acid or oleum. These products may be used directly as prepolymer ionomers which may be mixed with aqueous silicate solutions to Form the corresponding metal salt in situ. Alternatively, the sulphonation product nay first be partly or completely neutralised, e.g. 15 by the addition of amines, e.g. trimethylamine, triethyl- amine, methyl morpholine, pyridine or dlmethylaniline, or metal alcoholates, e.g. sodium tertiary butanolate or potassium isopropanolate. Neutralisation may also be carried out with solid melul oxides, hydroxides or carbonates or their 20 suspensions in diluents. For example, calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate and dolomite are particularly suitable.

Non-volatile, higher molecular weight tertiary amines are also particularly suitable Tor neutralisation because 25 they do not evaporate in the subsequent reaction with the alkali metal silicate solution. These tertiary amines are, in particularly alkoxylation products of primary or secondary amines or polyesters or polyacrylates which contain tertiary nitrogen atoms, as well as the known condensation products 30 based on epichlorohydrin and polyamines of the kind used, Tor example, for wet strengthening paper. Polycondensation products of weak basic amines or sterically hindered amines - 17 - 40271 nre preferred, because, when polyamlnes are used, (he viscosity increase may he too high.

The choice of suitable neutralising agents is also influenced by considering whether the neutralised or pnrtly 5 neutralised prepolymer ionoaer is required to be stable in storage over a considerable period or whether It is to be immediately reacted with the alkali metal silicate solution lit form the ionomer-si 1 iciu acid gel. If the rone I Ion is to be carried out immediately, neutralisation may be carried 10 out using tertiary amines which still contain reactive groups, e.g. Oil, Nlllt, or C0-N1I,,. If, on the other hand, prepolymers which are stable in storage are to be prepared, these groups should first be blocked, e.g. by reacting them with monoisocyanates. 15 The non-ionic-hydrophilic modification is carried out, for example, by using a hydrophilic polyether which contains groups which are reactive with isocyanate groups or by usirm a siloxane compound which contains nydrogen atoms which are reactive with isocyanate groups. 20 Suitable polyethers foi this purpose are polyethers containing OH end groups which have been synthesised from alcohols having a functionality of from 1 to 3 ethylene oxide and/or propylene oxide.

Otlcr polyethers or confounds containing polyether groups which 25 have been prepared by different methods, may of course, also be used according to the invention for preparing the prepolymers, provided they contain hydrophilic groups.

Monofunctional polyethers based on roonohydric alcohols with a molecular weight of, from 32 to 3000 and ethylene oxide 30 are particularly preferred because the non-ionic hydrophilic prepolymers obtained from them generally have a viscosity of less than 50,000 cl', which is convenient for working-up, and - 18 - 40271 preferably less than 10,000 cP. | Iteaction products of the above-aentioned polyisocyanates with aliphatic polycarbonate*! which contain hydrogen nloan which nr*' ri'iM'l Ivr willi iNiirymmlM group* nr«« it I no Niilinlili* prepolymera for the purpuwon of the present Invention.

Kxaaplcs of these polycarbonates Include polycarbonates based on diethylene glycol, dipropylene glycol and tetra-ethylene glycol.

Prepolyaers which contain a hydrophilic polyester segaent, e.g. a segaent of triethylene glycol or diethylene glycol and succinic acid or oxalic acid, are also suitable. Segaents of this type aay be destroyed in the course of the subsequent reaction with water glass, with the result that the inorganic component hardens and the organic coaponents Is rendered hydrophobic.

The hydrophilic centre aay also be introduced by incorporating a glycol, e.g. triethylene or tetraethylene glycol, preferably in combination with a highly hydrophilic isocyanate, such as a biuret di- or trl-isocyanate.

The hydrophilic group may be contained in the main chain or in a side chain of the prepolymer.

An ionic centre may also be present in addition to the hydrophilic—non—ionic segment. This ionic centre aay be present in the same molecule or another molecule. The morphology and interface chemistry of the diphasic plastics according to the invention may be Influenced as desired by means of such ionic-non-ionic combinations.

Known prepolyaers, in particular those based on aromatic isocyanates, may also be converted into non-lonlc-hydrophillc prepolymers by reactions carried out after the above mentioned process.

In particular, highly suitable prepolymers which hnve a high storage stability may also be obtained by reacting - 19 - aromatic isocyanates, e.g. tolylene diisocyanates, diphenyl-nethane diisocyanates and the known phosgenatinn products of condensation products of aromatic monoamines, in particular aniline, and aldehydes, such as Formaldehyde, with hydrophilic polyethers which contain groups which are reactive with isocyanates. These non-ionic-hydrophi1ic polyisocyanates, which, according to Llieir lit spectrum, still contain some urea and biuret groups and in particular urethane and/or allophanate groups which result from polyol modification, are particularly suitable for use as prepolymer ionomers.

For this non-ionic-hydrophilie modification it is particularly suitable to use phosgenation products of higher molecular weight nniIine-formaldehyde condensation products which have a viscosity of from 50 to 10,000 and preferably from lot) to r,,OOt> cl» at.

The isocyanates used may also be the reaction products ol' mono-, di- or poly-hal ides with metal cyanates. A particular advantage of this method is that the metal halide formed need not be removed from the reaction mixture. Combinations of the above-mentioned halides and metal cyanates may therefore be used quite successfully instead of the isocyanates. The polyhalides used may already have the character of oligomers.

Masked isocyanates may also be used. The conventional masking agenl, e.g. phenols, oximes, lactams, active methylene compounds, .t-butanol, sodium bisulphite and triazoles, are suitable for this purpose. The masked isocyanaLes also include the known nitrile carbonates and nitrile sulphites as well as amino-imides which contain zwi t.terions.

The masked isocyanates may be used either in addition to or instead of "normal" isocyanates. They arc particularly interesting for producing heat hardening systems with a long pot life or for systems which are required to be stable in 40271 storage. ! In conbinations of this type, the. isocyanate reaction nay' also take over the Function of Final hardening, For exanple aFter the heat-inddced ester hardening has already been completed. 5 The group or:vinyl nononers and/or other unsaturated polymer isable compounds which contain double bonds includes, in particular, the known nixtures oF unsaturated polyester resins and vinyl mftnoners sold commercially as "polyester resins" e.g. as described by II. Parkyn, in Composites 3 (1972), 10 No. 1, pages UiFTe Scientific and technical publ ication, tiui IdTord/Surrey.

The tern "unsaturated polyesters" as used herein includes the conventional polycondensalion products o iinsaLurated dicnrbnxyl ic acids with polyh.vdroxy conpounds, 15 in particular dioxy compounds, (see JBrksten et al "Polyesters and their Application", iteinhold Publishing Corp., New York, 1956).

Examples of suitable o,p-unsaturated dicarboxylic acids For preparing the unsaturated polyesters include: maleic acid, 20 Fumaric acid, ilaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, bromomaleic acid, dichloromaleic acid, hexahydrophthalic acid and their anhydrides. These may, if desired, be used as mixtures. For example with adipic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, 25 terephthalic acid, tetrachlorophthalic acid, hexachloro-endomethylene tetrahydrophthallc acid, hexahydrophthalic acid, endo-cis-bicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid, succinic acid, glutaric acid, tetrabromophthalic acid, naphthalene dicarboxylic acid, (e.g. as bis-alkylene glycol 30 ester), diphenylsulphondicarboxylic acid, (e.g. bis-alkylene-glycol ester), methylterephthalic acid, 'i-methyl-isophthalic acid, 5-methyl-isophthalic acid and their anhydrides. The conponents used For synthesislng the unsaturated polyesLers - 21 - <10 271 may also include monocarboxylic acids, for example acrylic and met line ry 11c acid, crotonic acid or benzoic acid as well as dimers or trimers of unsaturated Cj^-Coo fatty acids, e.g. linoleic acid, azelalc acid, sebacic acid, 2,2,4-trimethyl-5 adipic acid and trimellitic acid.

The saturated monocarboxylic acids used may be aliphatic, cyclocliphalic, aromatic or alkylaromatic carboxylic acids, e.K. a-ethyl-hexnnoic acid, stearic acid, the first distillation fractions of coconut fatty acid, benzoic acid, hexahydro-10 benzoic acid and £—JL-butyl benzoic acid. Advantages are obtained by using a u,p-ethylenically unsaturated mono-carboxylic acid, e.g. acrylic or methacrylic acid, in combination with exclusively saturated dicarboxylic acids. Polyesters which contain such condensed unsaturated carboxylic 15 acids, in particular acrylic and/or methacrylic acid, have no plasticising effect when used as additives in the polymerisable system because they can be polymerised with the systems in the hardening process. Other examples or unsaturated monocarboxylic acids include crotonic acid, sorbic aciil, oleic acid, soya oil 20 Tatty acids and ricineic acid. Substituted monocarboxylic acids such as ricinoleic acid and hydrogenated ricinoleic acid arc also of interest.

Kxamples of suitable polyhydroxy compounds include: ethylene glycol, diethylene glycol, hexamethylene-1,6-diol, 25 butane-1 ,'i-diol, 2-methylene-propane-l,3-diol, 2-methyl-propane-1,3-diol, triethyleneglycol, tetraethylene glycol tripropylene glycol, 1,*»-di-(2-hydroxy-ethoxy)-benzene, 1.3-di-(2-hydroxy-ethoxy)-benzene, cyclohexane-1,'i-diol, 1.4-bis-hydroxymethyl-cyclohexane, 11,1l-di-(hydroxymethyl)-30 9, lO-dihydro-fJlO-ethane-anthracene, (from acrolein, anthracene and formaldehyde), trime thylpei.tanediol, 'i.'i'-di-hydroxy-diphenyl-2,2-propane, hydroquinone, resorclnol, pyrocatechol, - 22 - 40271 di hydroxy <11 phenyl, riihydrodlphenylsulphide, dihydroxybcn*o-phenone, 4,4,-dihydroxy-dicyclohexyl-2,2-propane, propylene-1,2-glycol, dipropylene glycol, butane-1,3-diol, neopentyl glycol, trimelhylolpropancallylether, 2,2-bia-(4-hydroxy-5 nyclohcxyl)-propone, 2,2-bis-(4-hydroxyalkoxyphenyl )-propane, trimethylolpropane, glycerol, pentaerythitol, 2,2,4- and 2,4,4-trimethylhex<uie-l,6-dlol, 2,2-dimethylol-bicyclo-(2,2,1 )-heptene-5,3-methy 1-1,5-pentanediol, lsopropyl idene-bln-(p-plienylcnc-oxypropanol-(^) and bul-2-ene-l,4-dlol. Mono-10 hydroxy compounds, e.g. allyl alcohol, 2-ethylhexanol, methanol and ethanol, aay also be added in the synthesis of the unsaturated polyesters.

The unsaturated polyesters may also contain shorter or longer ether blocks. This may be achieved by adding ethylene 15 oxide, propylene oxide, styrene oxide or butylene oxide.

It is immaterial in principle whether alkoxylated glycols are used as starting materials or whether the epoxides are used directly in the polycondensation process. Mono-, di-and poly—isocyanates may also be used in the reaction, both 20 in subequivalent quantities compared with the ester resin, so that all the isocyanate groups are used up, and also in quantities sufficient to form NCO prepolymers. Copolymers of alkylene oxides and dicarboxylic acid anhydries of the type described in DDR Patent Specification No. 89,710 may 25 also be used as starting components.

Unsaturated polyester resins which contain amide groups may also be used, e.g. those which may be obtained by adding amino alcohols or amide diols. The preparation of such amide diols and unsaturated polyester amides has been des-30 crlbed, for example, in British Patent Specification No. 1,281,752. Examples include N,N'-dl-(6-hydroxycaproyl)-hexamelhylenedlaalne and N,N'-di-(2-hydroxyethyl)-oxamlde. - 23 - <10 37 I IHoIn which contain urc I liniic or men RroiipN lire also niiMmI»I<>, O.K. I, 3-dl-(b-hydroxyh«xyI )-urea; tris-(i!-hydroxynlky 1 )-isocyanates, which nay he nonofunctionally blocked as described in U.S. patent Specification No. I,b83,0'i8, are also 5 suitable.

Poly-unsaturated natural oils or their derivatives, e.g. soya oil, linseed oil, linseed oil fatty acid or linoleyl alcohol, may also be included for preparing the unsaturated polyester resin. The conventional alkyd resins 10 modified with unsaturated Tatty acids may also he used, optionally after they have been graTted with vinyl monomers e.g. acrylonitrile.

Quick-setting polyester resins which contain tertiary nitrogen aLoms, which may also be pnrtly quaternized, mny 1 *5 be used, e.g. the products obtained by condensing N,N-bis-3-hydroxyethylani1ine or N,N-bis-0-hydroxypropylanlline or the corresponding toluidines or other alkoxylated arylamines and alkylamines.

Polyester mixtures, e.g. oT condensates and/or precondensates which 20 give rise to brittle polyesters,(e.g. condensates and/or precondensates of Tumaric acid, phthalic acid anhydride, tetrachlorophthalIc acid anhydride, ethylene glycol or 1,2-propanediol) with precondensates which give rise to flexible polyesters, (e.g. precondensates of maleic acid, phthalic acid, di-, 25 tri- or tetra-ethylene glycol or. hexane-1,6-diol) are also particularly suitable.

The polyesters may also be modified by the addition of N,N'-bis—imides of unsaturated dicarboxylic acids, e.g. N,N'—ethylene—bis—maleic imide, N,Nhexamethylene—bis— 30 maleic imide, 2,4-bis-malelc imldotoluene and 1,6-bis- malelc imido-(2,2,4-trimethyl)-hexane and the reaction products with diamines or polyamlnes. Exceptionally high heat resistance is thereby obtained. - 24 - | 40271 The polyester resins uy also be aodifled with mono— funotlonal or polyFunctional.epoxy compounds. This mod- I ification has the effect, for example, -of Improving the compatibility of the resins with the thermoplasts added 5 but it also improves the bond between the resins and the Inorganic phase which may, for example, contain diamines or polyamines. - Another possible modification Involves reacting the unsaturated polyester with dicyclopentadiene. 10 (Exceptionally gd>d compatibility with the Inorganic phase is obtained by reacting the unsaturated polyester wjih sulphur trioxide, phosphorus pentoxide, polyphosphorlc acid or sodium hydrogen sulphite.

Polyester resins which may also be used according to the 1*5 present process are unsaturated alkyd resins and, for example, reaction products of butadiene oils, (with or without functional groups), unsaturated fatty acid esters and maleic acid anhydride and, optionally, other ethylenically unsaturated monomers. liO Polyesters of the type described, e.g. in British Patent Specification No. 806,730, which are modified wilh colophony, abietic acid or their Diels-Xlder products are also suitable.

The ester resins may be modified with monolsocyanates of polyisocyanates in accordance with DBP No. 940,018 or 25 with an excess of isocyanates to form NCO prepolymers.

The acid number and molecular weight of the unsaturated polyesters used, which are predominantly linear but may also be branched, may vary within wide limits, e.g. from 0.1 to 120 In the case of the acid number and from 400 to 30 5000 in the case of the molecular weight. It is preferred to use polyesters wilh acid numbers of from 10 to 80 and molecular weighs of from 600 to 3000. - 25 - 40271 Combinations of different polyesters may, of course, also be used, e.g. hard, unsaturated polyesters and more flexible, only slightly unsaturated polyesters.

Polymerisable oligomers which are equivalent Lo poly-5 esters resins include epoxyacrylale resins, polyester acrylates e.g. or bisphenol A and acrylic acid, polyether acrylates and polyurethane acrylates. Polyurethane acrylates are generally reaclion products of low molecular weight or higher molecular weight diisocyanates or polyisocyanates 10 with monomers which contain a polymerisable unsaturated double bond and Zerewitinoff active hydrogen atoms in one and the same molecule. The NCO groups may be completely or only partially. reacted wilh the monomers, e.g. hydroxy-ethyl acrylate, hydroxypropy1 acrylate or methacrylate and fi acrylamide or mcLhacrylamide.

Examples of suilable ester acrylates and ureLhanc acrylates may be found, e.g. in German Ofrenlegungsschrlft No. 2,258,211.

Adducts of hydroxyethyl or hydroxypropyl acrylate or 20 methacrylale with commercial phosgenaiion products of aniline-formaldehyde condensates are particularly preferred.

The unsaturated resins disclosed in German Offenlegungs-schrift No. 2,164,386, which are formed by isocyanate lengthening of reaction products of diepoxides and a,P-unsalurated 25 carboxylic acids or dicarboxylic acids or of reaction products of dicarboxylic acids and unsaturated glycidy) compounds are also suitable starting materials.

Unsaturated polyesters are preferably used in combination with vinyl monomers, e.g. in ratios of from 5:95 to 30 H5:15.

Suitable vinyl monomers, are in particular, styrene, a-methylslyrene, vinyl acetate, allyl acetate, diallyl- - 26 - ! 40271 . i phthaiate, trichloroethylene, _t-buty.lstyrene, 2-hydroxy-ethylmethacylate, divinylbenzene, chlorostyrene, methyl methacrylate, vinyl toluene, propylene glycol nonoacrylate, aerylamide, butylmcthacrylate, cyclohexylmethacrylute, •> ethyl acrylntn, ethyl hexyl acrylate, acrylonitrilo, triallyliHocynnurnte, vinyl benzoate, divinyl adipate, diallylisophthalate, and naleic acid esters, e.g. or lower alcohols, e.g. cthanol, butanol, or ethylhexanol and 1!-alkyl-'i-norbornone-lf-carboxylic acid, (alkyl ester), N-10 vinylpyrrolidone, maleic acid iaide or N-vinylcarbazole.

The addition or acrylic or methacrylic acid glycidyl esters improves the flexural strength.

Partial-esters of polyhydric alcohols and anhydrides or unsaturated dicarboxylic acids, e.g. styrene sulphonic l1} acid, and phenyl sulphonic acid esters or acrylic and methacrylic acid may also be used together with the above-men Li oned vinyl compounds. These products, which may be neutralised by the inorganic phase or by the addition of inorganic and/or organic bases, result in an exceptionally 20 good bond wii.h the inorganic phase.

In some cases, the process may also be carried out in the absence of polyester resins. Solvent-free polymerisation of vinyl monomers may also be initiated quite safely by diluting with the aqueous silicate solution. The vinyl 25 monomers suitable for this purpose include, e.g. styrene, vinyl toluene, acrylates and methacrylates, optionally in combination with maleic acid or maleic acid anhydride, as well as acrylonitrlle with acrylic acid. Monomers containing acidic groups are preferably used in order to ensure surricient 30 interraction with the inorganic phase and achieve higher Impact strength.

Such solvent-rree polymerisation of vinyl monomers in the absence or polyester, ester alkyd and similar resins - 27 - 40271 1h particularly interesting if the lsocyanate used as component (b) contains unsaturated double bonds or cine ihylene groups (or phenylogous nethylene groups) which arc capable of nrarting. 5 IT a high proportion or vinyl monomers is used, tlii» viscosity may be increased and the shrinkage reduced by also using polymers such as high pressure polyethylene, polystyrene, AllS copolymers, styrene copolymers with acrylic acid or methacrylic acid or esters or with mnleic acid, 10 polyvinyl and polyallyl esters and ethers, ethylene/vinyl acetate copolymers, vinyl chloride/vinyl acetate copolymers, alkylacrylale/alkylmelhacrylale copolymers, e.g. methyl-methacrylate/hulyl acrylnte copolymers, cellulose aceto-liutyratr, cellulose acetoproplonate or polyurethanes. Polymcru 11 which contain -COOII, -So^ll or the corresponding salt groups and which also have an emulsiTying action are particularly advantageous. The polyurethanes preTerably have molecular weights below 30,000 ami contain -Oil, -C001I, or urethane end groups. 20 Polydiene esters of the kind described e.g. in Herman or t'enlegungsschri f t No. 2,160,722 are suitable Tor increasing the Tlexibility.

Substituted ureas as described in U.S. Pntent No. 3, 632,668 and analogously synthesised thixotropic compounds, 25 e.g. ureas and urethanes of diisopropyl and triisopropyl-phenyl-isocyanate may also be used as thickeners.

Particularly interesting Tor use in the present process are polyester resins which are known to have a high resistance to alkalies, e.g. reaction products of phenoxyalcohols, 30 ethy1ene-1,2-dicarboxylic acids and formaldehyde, (see DUlt Patent No. 83,650 and P. Penczek in Plaste und Kautschuk 19 (1972), No. 1, page 3).

The factors which afreet the chemical resistance and in - 28 - 1 40271 particular resistance to aikalles are known. In many I cases the inroraallon given in the literature also applies, in principle, to the combinations or the present invention which conlaln polyesters. Tor example the combination dis-5 closed in Cerman orTenlegupgsschriTt No. 2,258,86*), are suitable.

Unsaturated products analogous to polyester resins, which may also be used in the process, are the corresponding ester resin urethanes and oligoether urethanes, e.g. reaclion 10 products or polyether diols, diisocyanates and allyl alcohol, and isobutylene/isoprene copolymers.

Products or this kind may, in the same way as unsaturated polyester resins, be hardened by the action of the alkaline silicate solution in the presence or polyruncLional hydrazide 15 halidos, (nitrile imino precursors), (see U.S. Patent SpeciTication No. 3,671,475).

The mixtures which contain unsaturated resins and/or vinyl monomers may be stabilised by the addition of conventional inhibitors, e.g. hydroquinone, toluhydroquinonc, 20 phenacine, tetrabromocatechol, cobalt, zinc, or aluminium salts or N-ni trosohydroxylamines, (see Uerman Of I'enlegungs-schrift No. 2,215,946), £-benzoquinone, £-jt-bu tyl-pyroca techol, chloranil, naphthoquinone, copper compounds or j>—nitroso-dimethylani1ine. 25 Thiodiglycols, such as 2,2'-dihydroxydiethylsulphide, and nitroxides of the kind described e.g. in U.S. Patent Specification No. 3,682,875, e.g. di-^-butylnitroxide, arc also suitable stabilizers.

The conventional Tree—radical initiators may be used 30 Tor hardening compositions which contain polymerisable polymer precursors, e.g. dicumyl peroxide, di-^-butyl perbenzoate, cumene hydroperoxide, ^-butylperoxide, per-oxymethy1ethyl ketone, 3,5-dimethyl-3,5-dihydroxy-l,2- - 29 - peroxycyclopentane, l», 5-dimethyl-2, 5-bis-(li-ethyl-hexanoylperoxy)-hexane, cyclohexanone peroxide, ^t-butyl peroctoate, azoisobutyrodini trile, lauroyl peroxide, t-but.yl peroxypivalate, succinic acid peroxide and, r( particularly, d I beir/.oy I peroxide.

The hardening catalyst should preferably be insoluble in water.

The hardening catalyst is generally used in quantities of from 0.1 to 5jt, by weight, based on the sum of unsaturated 10 polyesters plus monomers. Which catalysts are the most suitable for a particular reaction mixture may, in many cases, lie determined by the methods indicated by the manufacturers of such Initiators, (sen e.g. HroschDren der I'eroxiri— Chemie (imbll, D-8023, 1101 lriegelskreuth bei MQnchen). I1) Suitable hardening accelerators are, in particular, the •conventional cobalt and vanadium salts, e.g. cobalt naphl.hcnate particularly when used in combination with kel.o peroxides; known N,N—tlialkylarylamines, e.g. N,N—dimethyl amine or dimethyl £-toluidine; imides e.g. succinimide, phthalinimide, and 1»0 benzoic acid sulphimide and thn conventional redox systems, e.g. sulphites and dithionites.

Metal salts of alky1phthalates, e.g. Co-, Cr-, Cu-, Ke-, Mn-, Ni-, Ti-, and vanadyl-bis-(n-butylphthalate) are particularly suitable hardening accelerators for compositions 25 which contain acrylates.

The various methods of hardening ester resins are known to one skilled in the art, (see e.g. .J. Schneider, Kunstst.off-Itundschau 19 (1972), No. 11, pages 587,591).

Cold hardening or heat hardening may be preferred, 30 depending on the given purpose.

According to a particularly preferred method of carrying out the invention, the precursors of a polyurethane and/or polyurea together with precursors of a hardened - 30 - 4 0 371 polyps tor resin or the Itlnd disc lotted, e.g. in British I'iiLkiiL Spnriricallon Noh; 1 ,i!7U ,9H'i und 1,279,673 and in lieratui OfrenlegungNHchrl ft No. L'jliW),!')') are used tin the liquid organic pliuse.

In contrast to the prior art, however, in the process i • : according to thin invention the reaction ot at least one I of the components in the mixture with the alkali aetal .silicate soluLion to form a diphasic or multiphasic xerosol which has the characteristic properties or a diphasic compos! ie material is decisive. Although polyaddition to form a polyurethane in the usual sense or a reaction of the precursors of a polyurethane with the precursors ot a hardened polyester resin is possible, it is not necessary and does not always occur.

Aiong the phenol resin condensates and/or precondensates are also liidiried the conventional resols or novolaks in combination wilh hardeners. Examples of suitable products may be found, e.g. in llouben-Weyl, 'ith Edition, published by E. MQllor (1963) Volume XIV/2, pages 193-319. In general, these products are condensates and/or precondensates of phenol compounds with aldehydes, in particular formaldehyde.

The phenolic compounds used are preferably phenol, o-, m- and £-cresol, xylenols, a- and 0-naphthol, alkyl-phenols and arylphenols, e.g. ^-hutylphenol, £-phenyl-phenol, jwionylphenol, j*-chlorophenol, £-bromophenol, bisphen-ol A, 'i,4'-di hydroxy di phenyl, 4,'<'-dlhydroxydiphenylsu1phone, pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloro-glucinol, dihydroxytoluenes and their mono-alkyl or mono-aryl ethers as well as commercial mixtures which contain mainly phenolic components. - 31 - 40271 Particularly suitable phenol resins are obtained by alkfx ylating convenlionul novolaks and resols wilh ethylene oxide and propylene oxide. This modiTication is capable of reducing the solubility, or the phenol resins in the alkali metal silicate soluLion but increasing the dispers-II)i 1 i ty.

I'henol re.sins which have been prepared Trom reaction mixtures containing me thy lot-containing polyesters, polyester ureLhanes or polyether urethanes, (iJennan OfTenlegun&s-schrirt No. 1,770,068), are also suitable Tor use as starting materials, (sec IJ.S. Patent Specification No. 3,647,919), as are also phenol resins which are modified withf-capro-lactam, (U.S. Patent Specification No. 3,639,658).

Phosphites may be included Tor colouring purposes.

Acid amides e.g. acetaraide, N-methylacetamide, adiplc acid mono— and di—amide, oxalic acid diamide, 6—hydroxy-caproic acid amide, caprolactam, acetanilide, benzamide, N-acctylglycerol, as well as suTTiciently soluble oligo-mides or polyamides based e.g. on trimethyl hexamethylene-diamine, diamino-dicyanhexylmethane or methyl adipic acid may also be included. The conventional starting materials Tor preparing aminoplast condensates are also suitable, e.g. as described in llouben-Wey 1, 4th Kdition, publishers K. Mttllcr, 1963, Volume XIV/2, pages 193-319 and in «\. Ilachmann and Th. Hertz: Aminoplaste, 1967. Ureas, methylurea, ethylene urea, melamine, acetoguanamine, benzoguanamine, dicyandiamide and cyanamide are preferred.

The phenol resins used may be blended with bituminous 40271 ■asses, e.g. with natural asphalt, petroleum bitumen, coal tar, wood pitch, wood tar, coal tar pilch, lignite t.nr and lignite pitch.

The preTerred phenol resins contain quaternary ammonium, *> tertiary sulphonium'j carbocyl and sulphonic acid groups.

They are obtained in convenlional manner by incorporating, by condensation, the corresponding acids or amines, e.g. phenol sulphonic acid, amidnsulphonic acid, glycine, aminocaproic acid, lignin sulphonale, sulphite waste liquors, 10 dimelhylaminophenol or diethanolamine, or by subsequently modifying the phenol resins, e.g. by reacting them wiLh propiolnctone, propanesultone, sulphur trioxide, oleum or sulphuric acid. in particular, ionic nodiTication oT hydrophobic phenol 11 resins, is Trequently carried out in this way. 11 is particularly preTerred to use those phenol resins which are insoluble or at least not completely soluble in the alkali me Lai or ammonium silicate solution, but may easily be dispersed. 20 Although, iT substantial quantities oT water-insoluble isocyanates or isocyanate prepolymers or other organic re-actants are present, one may also use a phenol resin which is soluble.in alkalies and thus bring about organic modlTl-cation oT the inorganic phase, it is necessary to use 2*> phenol resins which are insoluble in alkalies IT the organic reactants arc predominantly soluble in water or alkalies.

This is particularly necessary IT only very small quantities or isocyanates are used or IT water-soluble, and thereTore highly reactive, isocyanates are used because one should in 20 all cases obtain an inorganic-organic diphasic or multiphasic system.

The preTerred phenol resins which are at least partly 40271 insoluble in alkalies are obtained by including hydrophobic components, in particular xylene, styrene, a-methylstyrene, vinyltoluene, acet^ldehyde or furfurol. Particularly suitable modifying components are styrenised phenol used as phenolic component and furfurol used as aldehyde component.

Hydrophobic resols which have been alkoxylated with propylene oxide, ethylene oxide or butylene oxide are also suitable.

The preferred amino resins are condensation products of aldehydes, e.g. formaldehyde, acetaldehyde, propionaldehyde, butyl aldehyde, crotonaldehyde, chloroacetaldehyde, bromoacetaldehyde, chloral or benzaldehyde, with condensable ureas, acid amides, sulphonamides, urethanes, ureides, biurets, or aminotriazines, optionally in combination with known co-condensable compounds, e.g. the above-mentioned phenols polyphenols, aromatic hydrocarbons, aromatic amines, active methylene compounds and react ion products of urea or melamlnc with diamines or polyamines.

As in the case of phenol resins, it is preferred to use those resins which form an ionic group in the alkaline medium. Introduction of these groups may be carried out in a similar way as described for the phenol resins.

Particularly suitable for use in the process according to the present invention are amino resins which have been modified with isocyanates or with NCO-propolymers. These resins may be regarded as urethane prepolymers which contain amino resin end groups. Products of this type have been described fully in German Offenlegungsschrift Nos. 1,770,068 and 1,913,271. The products are preferably ionically modified as described in the said documents although they may have a non-ionic structure. Modified phenols or phenol renins may bo prepared in( nnaltxjoun manner.

Condensation and/or pre,condensation of the resins is preferably carried out in an alkaline medium, using the conventional condensing agents. The addition of alkali metal, ammonium or guanidinium silicates as condensing agents is particularly preferred. Condensation and/or precondensation may also be carried out in an acid range. Quick hardening novolak resins are prepared, e.g.,in the presence of ainc soaps or lead soaps.

The condensates and/or precondensates are preferably insoluble or only partially soluble in water or aqueous alkalies,but are easily dispersed in these media. Soluble condensates and/or precondensates may be used only if at least one of the other components in the aqueous silicate solution is insoluble to ensure the formation of a discrete organic phase.

Conventionally, the phenol resins or amine resins are hardened under alkaline or acidic ccmditions with heating.

In the case of alkaline hardening, the alkali metal silicate used as inorganic phase serves as hardener. Epichlorohydrin or 1,3-dichloropropan-2-ol may be added as accelerator.

In the case of acid hardening, care must be taken to ensure that the acidic catalyst is not transferred completely to the inorganic phase. It is therefore preferable to use as hardeners relatively hydrophobic acids or acids which may be incorporated, e.g. phenol-sulphonic acids,naphthol- sulphonic acids, toluic acid, trimellitic acid pyromellitic acid metllitic acid and benzophenone tetracarboxylic acid and their anhydrides.

Other suitable hardeners include* e.g.the combinations 40271 described in German Offenlegungsschrift No. 2,llo,264,e.g.formamide/ tuityrolnctone/boric acid or foroamide/roraic acid or carbonic nci(l esters/boric acid.

The addition of heterocyclic acids, e.g. carboxylic acids or pyridine, Turan, thiophene or pyrrole, increases the ritiidii-y of the systems, especially in the case or systems which have a high Tiller content.

Numerous known Tormulations have been developed to ensure rapid hardening with as little evolution or Torm-nldetiyde as possible, Tor example the combinations proposed in U.S. Patent SpeciTication No. 3,637,561.

The combination oT a resol with a novolak sulphonic acid is part.icularly suitable. The novolak sulphonic aeid in this combination serves bolh as reactant and as hardener.

In this method, the novolak sulphonic acid is preferably used in excess so that. it. may also bring about hardening <>l the inorganic phase.

Higher molecular weight sulphonic acids may also • e combined with conventional low molecular wwiglit hardeners which are capable oT dlTTusing into the inorganic phase.

Other higher molecular weight hardeners which have less tendency to diTTuse may also be used for the organic resin phase, e.g. copolymers or vinyl sulphonic acid, polyconden- * sates of amidosulphonic acid and polymers of styrene sulphonic acid.

Hardening is carried out in the presence or phenol resins preTerably with heating. The initial heating is, in many cases, provided by the reaction or the isocyanate.

Additional heat may be produced within the system by polymerisation or nut ncondensat ion oT suitable additives, furTuryl alcohol or 2,3-dihydro-'iH-pyran-2-carboxy Ini e in combination with strong acids, (see German Offenlegungsschrift No. 2,105,'«95). - 36 - I 4027 1 Other conventional methods of hardening by applying external heating may, of course, also be employed. External application of heat is particularly necessary when masked isocyanates are used. 5 Precursors of epoxy resins may also be used in the process according to the present invention. Compounds I suitable for this purpose have been described, e.g. in llouben-Wcyl, 4th Edition (1963). See also E. W. Garnish, Composites 1972, 104-112, Iliffe Scientific and technical lO publication, Guildford/Surrey, Volume XIV/2, pages 462-538, The polyepoxides used are preferably the known reactions products of various diphenols or polyphenols with epichlorohydrin. Monoepoxides may also be included for modification. Preferred polyphenols are the condensation 15 products of phenols and cresols with aldehydes, in particular with formaldehyde or acetaldehyde, or ketones, such as acetone or methyl ethyl ketone. Bisphenol A and liquid novolaks are particularly preferred. Aliphatic polyepoxides, e.g. vinyl cyclohexene diepoxide, dicyclopentadiene 20 diepoxide and epoxidised polybutadiene, are frequently also added to lower the viscosity. Since the polyepoxides are hardened in an alkaline medium, epichlorohydrin itself may also be added, optionally in - 37 - t 40271 combination with polyphenols. Liquid polyepoxides are also particularly preferred, e.g. those which may be derived from aliphatic or aromatic amines. Reaction products of epichlorohydrin and aniline, toluidines and diaminodiphenyl 5 methane and commercial mixtures of aniline-formaldehyde condensation products are particularly suitable.

Highly reactive hardeners, such as diprlmary amines, are particularly suitable for hardening. Suitable combinations with which rapid hardening may be effected are lO known. In particular, they include the combinations of diethylene triamine, triethylene tetramine, tetraethylene penamine or their partially alkylated products or hydrogenation products of acrylonitrile adducts with primary amines, N-aminoalkyllactams, in particular N-aminopentylcaprolactam, 15 oligoamidamines e.g. obtained from aliphatic polyamines and dimcrised or trimerised unsaturated fatty acids, dicyan-diamidc, polycarboxylic acid polyhydrazidos and commercial mixturesof aniline-formaldehyde condensates. Combinations of polyepoxides with amines in which one 20 component has an ionic group in a basic medium, e.g. an aminocarboxylic acid or quaternary ammonium amine, are also particularly suitable.

Suitable accelerators are, in particular, tertiary amines. - 38 - 40371 Itcacfion products or acid anhydrides with polyaaines jim (losn llu'il «*.»•.. in U.S. rntrni Spec11'i»*nI imi Ni>. are nImi> excellent lint'dcneis Mince (li«»y rlsi' to nixlurcN f * wliirli are stable in NlnrnRe ami at elevated tempera!ures anU . r> which simultaneously harden both the inorganic and the organic phase. * other haloepoxyalkanes and dihalohydroxyalkanes aay, oi° course, also be used instead or or in addition to epichlorohydrin.

IO IL is an essential requirement of the present process that a mixture or at least three components must be provided, namely an alkali metal silicate in aqueous solution, an isocyanate and one of the above-mentioned polymer precursors which are capable or polymerisation and/or polycondensation. lr> The proportions in whtch the three components are present is not critical and may vaiy within the limits indicated. In particular, there need be no stoichiometric relation between the three components since each component in principle hardens independently or the others although they may, or 20 course, influence each other lo some extent.

The proportion of aqueous alkali metal silicate solution present should be at least 20£ and not more than &r)$, prererably from 30 to 70jt by weight. The lowertlimit is suitable in particular Tor concentrated solutions and the upper limit. L"5 for low percentage solutions. The solids content or the silicate solution in at least 20Jt and not more than 70£, prererably Trom 32 to 5'ijt. The amount or solid alkali metal silicate (calculated) based on the total mixture should generally not be less than lOJt and is preferably 30 20 to 70^. A proportion or less than lOjt is, or course, possible,but the particular advantages of the present invention then no longer fully come into effect. - 39 - 40271 The proportion or isncynnnte cliould he Trom 5 to 70jf, hy weight of the tol.nl mixture, preferably from 10 to 'jOjt.

In the case of low molecular weight isocyanates it tends to lie nl I he lower end of the range and in the case of higher r> molecular weight isocyannLes and prepolymers il. is prererably in the middle or upper regions or the given range. The isocyana Le proportion may, of course, also be less than r>%, especially in the case or low molecular weight products, lint the specific advantages or isocyanate hardening accon-10 panicd hv increase in viscosity and simultaneous hardening or the inorganic phase are then brought out only to a slight ex ten I.

The proportion or polymerisable and/or polycoiidensable polymer precursors should be from lO to 7r>% and is I" preTerably from L'O to 70Jt, based on the total Mixture. The proportions may l»e slightly above or below those limits but in that case there will lie some loss in the quality of t bo pro tlu i! I.s.

Hy"total mixture" us used herein in this con I ox I t JO is meant the sum or the three constituents mentioned above, regardless or any additional components, e.g. Ii.i rdcnci s, add i t i ves, flame retarding agents or fillers. The j socvana I «• used m.iy quite well "double" as a component of croup i« i i.e. as a polymerisable and/or polycondensable polymer precursor. This applies e.g. in the case of vinyl isory/ina i e, his-(2-isocyanatoethy1)-fumarate, adducts of diisocyanates and resols, epoxy isocyan-ites. The quantity of such products may amount to rrom 5 to 80JI, by weight ol" the total mixture.

A solution or component (b) and of component (c) oi 30 mixture or these two components may also be used accord m.-to the invention. This is a particularly important ft.tu.. or the invention ir component (b) consists or commoriiil distillation residues ol' aromatic polyisocyanates, it - 40 - j 40271 ! ! particular those obtained froa the coaaeroial production or tolylene diisocyanate and diphenylaethane diisocyanates, or ir component, (c) Is styrene, optionally aixed with other . '' , ' | unsaturated aonoaers. The reason for this is that the sur- i ' prising observation has been aade that these residues or polyisocyanates are particularly readily soluble in styrene, for exaaple solutions containing froa 20 to 50£, by weight, of residues of tolylene diisocyanate distillation in styrene are low viscosity solutions. Viscous solutions aay even be prepared with concentrations of distillation residue of up to 75?» by weight.

It has also been round that these solutions alx wilh aqueous alkali aetalor .umurtiuii silicate solutiorato form emulsions which harden in the presence of a styrene hardener to fora hard diphasic plastics. The presence of such a strong alkaline alkali aetal silicate solution aay be relied upon to coapensate for the vatlations in activity of the residue isocyanates, so that the reaction will take a reproducible course.

The reaction mixtures of the present process aay be aodified in various ways by additions of polyols, unsaturated polyester resins, polyisocyanates, blowing agents and fillers whereby interesting and extreaely economical inorganic-organic plastics become available which, by virtue of their excellent fire resistance, may be used, above all as building materials and also as binders in a wide range of applications The residue Isocyanates which would be suitable are particularly the residues obtained froa the distillation or tolylene diisocyanate, particularly those which still contain small quantities of free tolylene diisocyanate and/or adducts of tolylene diisocyanate. Distillation residues of this kind may be obtained, for example, by the process - 41 - 40271 described in German Offenlegungsschrift No. 2,035,731. The distillation residues described in German Offenlegungsschrift No. 2,123,183 are also suitable as well as solutions of these residues in phosgenation products or aniline formaldehyde 5 condensates, which have also been described in German Patent Application No. 2,123,183.

The highly viscous and resinous residues obtained from the distillation of 4,4'-diisocyanatodiphenylmeLhane from crude phosgenation products of aniline-formaldehyde conden-10 sates are also suitable. The isocyanate content of these residue isocyanates is generally from 15 to 35S&» preferably from 25 to 32*.

Another important criterion of tAe invention is that diphasic or multiphasic composite materials are formed which 15 are macroscopicAlly homogeneous but have a microscopically or submicroscopically distinctly visible morphology. The disperse phase generally has dimensions of the order of from 20 mpi to 100 p, preferably from 100 mp to 10 p.

The organic and inorganic phases need not. be completely 20 incompatible with each other to Lhe extent, for example, ol being completely immiscible. In fact, it is preferred to use mixtures which have a limited compatibility with each other so that emulsions are easily obtained. The phases may also be soluble in each other to a limited extent so that. 25 '-he silicate phase contains part of the organic material and/or the organic phase contains part of the inorganic material, but in no case may the organic component be completely dissolved in the silicate phase. If this does happen In the case of certain phenol resins or amino resins, then at 30 least the isocyanate component should form a separate organic phase.

If these criteria are observed, materials having the - 42 - I 40 271 I - characteristic advantages or'th^ diphasic systea are obtained without the disadvantage or insufficient bonding at the interfaces.

In addition to the main components aentioned above, 5 coapounds containing Zerewitinoff active hydrogen atoms may be used as additional reactants for the lsocyanate coapounds, in particular polyols,such as ethylene glycol or condensates f • » or ethylene glycol, butane-1,3-diol, butane-1,4-diol, butene diol, propane-l,2-dlol, propane-1,3-diol, neopentylglycol, 1<> hexanediol, bis-hydroxyaethyl-cyclohexane, dloxethoxyhydro-quinone, dioxethyldian, bis-glycol terephthalate, succinic acid dl-p-hydroxyethylcutide, succinic acid di(N-aethyl-(3-hydroxyethyl)]-aalde, 1,4-di-(P-hydroxy-aethyl-aercapto)-2,3,5,6-tetrachlorobenzene, 2-aethy1ene-1,3-propanedlol and '5 2-aethy1-1,3-propanediol; also coapounds generally with a molecular weight of from 400 to 10,000 which contain at least two hydrogen atoms capable of reacting with isocyanates.

Apart from compounds which contain amino groups, thiol groups or carboxyl groups, these compounds are preferably polyhydrox-20 y1 compounds, in particular compounds with froa 2 to 8 hydroxy! groups and especially those having a molecular weight of frcin 800 to 10,000 and preferably from 1,000 to 6,000, e.g. polyesters, polyethers, polythloethers, polyacetals, polycarbonates or polyester aaides which contain at least two, generally 25 from 2 to 8, but preferably froa 2 to 4 hydroxyl groups, of the type which are known for producing both homogeneous and cellular polyurethnnes.

The hydroxyl group-containing polyesters may be, for example reaclion products of polyhydric alcohols, preferably 30 dlhydrlc alcohols, with the optional addl tlijn of trlhydrlc alcohols and polybasic, preferably dibAsic, carboxylic acids. Instead of the free polycArboxyllc acids, the corresponding - 43 - 40271 carboxylic acid anhydrides or corresponding polycarboxyllc acid esters of lower alcohols or mixLures thereof nay be used for producing the polyesters. The polycnrboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or hetero-5 cyclic and may be substituted, e.g. with halogen atoms, and/or 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, hexa-10 hydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric: acid anhydride, mnlcic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric Tatty acids, such as oleic acid, optionally mixed with monomeric fatty acids, l1} dimethyl terephthalate and bis-glycol terephthalate. Unsaturated polyester resins may often be included in the present process. Suitable polyhydric alcohols include e.g. ethylene glycol, propylene-1,2- and -1,3-glycol, butylene-1,4- and -J,3-glycol, hexane-1,6-diol, octane-1,8-diol, 20 neopentyl glycol, cyclohexane dimethanol (1,4-bis-hydroxy-methylcyclohexane), 2-methy1-1,3-propanedlol, glycerol, trimethylolpropnne, hexane-1,2,b-triol, bui.ane-1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, me thy1glycoside, diethylene glycol, triethylene 25 glycol tetraethyleneglycol, polyethylene glycols, dipropyl-ene glycol, polypropyleneglycols, dibutylene glycol and polybutylene glycols. The polyesters may contain a proportion of carboxy] end groups. Polyesters oT lactones, e.g. f-oaprolac tone, or hydroxycarboxylic acids, e.g. U)-hydroxy-3(> caproic acid, may also be used.

The hydroxyl group-containing polyethers which may be used according to the Invention and which contain at least 2, - 44 - 40271 generally from 2 lo 8 and preferably 2 or 3 hydroxyl groups are also known and may be prepared e.g. by the polyaerisation of epoxides, e.g. ethylene oxide, propylene oxide, butylene oxide, letrahydrofuran, styrene oxide or 5 epichlorohydrin, each with itself, e.g. in the presence of IlKj, or by the addition of these epoxides, optionally us mixtures or successively, to starting components which conLain reactive hydrogen atoms, e.g. water alcohols or amines, e.g. ethylene glycol, propylene-1,3- or 1,2-glycol, It) lr I mo thy lol propane, 4,4'-dihydroxy-diphenylpropane, aniline ammonia, ethanolamine or ethylenediamine. Sucrose polyethers such as those described e.g. in German Auslegeschrlften Nos. I,17'>,358 and 1,1)64,938 may also be used according to the invention. It is frequently preferred to use those poly-15 ethers which contain predominantly primary Oil groups (up to 90*, by weight, based on all the OH groups present in the polyether). Polyethers which have been modified with vinyl polymers, e.g. the polymers obtained by the polymerisation of styrene or acrylonitrile in the presence of polyethers, 20 (U.S. Patent speciTication Nos. 3,383,351; 3,304,273; 3,523, 093 and 3,110,695 and German Patent SpeciTication No. 1,152, 536), and polybutadienes which contain Oil groups are also sui table.

Among the polythioethers there should be particularly 25 mentioned the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amlnoalcohols. The products obtained are polythio mixed ethers, polythioether esters of polythioether ester amides, depending on the co-30 components.

Suitable polyacetals are e.g. the compounds which aay be prepared Trom glycols, e.g. diethylene glycol, triethyl- - 45 - 4 0 271 i»n«* Rlycol, '«,V-ili»xethoxy-di phenyl dimethyl me thane or hexane-tliol and fornnldehyde. I'olyacetals suitable for the purpose »r the invenlion nay also he prepared by polymerising cyclic ace tills. t - 46 - 40271 Suitable hydroxyl group-containing polycarbonates are known and aay be prepared, e.g. by reaotlng diols, e.g. propane-1,3-dio1, butane-l,4-diol and/or hexane-1,6—dlol or diethylene glycol, triethylene glycol or tetraethyl-5 eneglycol, with diarylcarbonates, e.g. dlphenylcarbonate or phosgene.

Suitable polyester aaldes and polyaaides Include, e.g. the predominantly linear condensates obtained froa polyvalent saturated and unsaturated carboxylic adds or their 10 anhydrides and polyvalent saturated and unsaturated aalno alcohols, diamines, polyaalnes and alxtures thereof.

Polyhydroxyl compounds which already contain urethane or urea groups and modified or unmodified natural polyols, e.g. castor oil, carbohydrates or starch are also suitable. 15 Addition products of alkylene oxides and phenol-form- aldehyde or urea-foraaldehyde resins may also be used according to the present invention.

Examples of these compounds which aay be used according to the invention have been described e.g. in 20 High Polymers, Volume XVI, "Polyurethanes, Chenlstry and Technology", published by Saunders-Frlsch, Intersclence Publishers, New York, London, Voluae I, 1962, pages 32 - 42 and pages 44 - 54 and Voluae II, 1964, pages 5-6 and 198 -199 and in Kunststoff-Handbuch, Volume VII, Vleweg-HSchtlen, 25 Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

Catalysts are often used In the process according to the Invention. Suitable known catalysts Include e.g. tertiary amines, e.g. triethylaalne, tributylamlne, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorphollne, N,N,N',N'-tetraaethyl-30 ethylenedlamlne, l,4-diaza-bicyclo-(2,2,2)-ootane, N-methyl-N'-diaethylaalnoethylplperazine, N,N-dlmethylbenzylaalne, bis-(N,N-diethylamlnoethyl)-adipate, N,N-dlethylbenzylamlne, - 47 - 40271 pentaaethyldlethylenetrlaaine, N,N-diaethylcyclohexylaaine, N,N,N,,N,-t«trftBethyl-l,3-butanedlaain«, N,N-dlaethyl-0-phenylethylamlne, 1,2-diaethy1-imidazole, and 2-aethyl-laldazole. 5 Suitable tertiary aalnes containing hydrogen a tons which ore reactive with lsocyanate groups Include, e.g. triethanolaalne, trllsopropanolaalne, N-nethyl-diethanolamine, N-ethyl-diethanolaalne, N,N-dlmethyl-ethanolaalne and their reaction products with alkylene oxides, e.g. propylene oxide and/or 10 ethylene oxide.

Sllaaalnes which contain carbon-slllcon bonds are also suitable catalysts, e.g. those described In Geraan Patent Specification No. 1,229,290, for exaaple 2,2,4-trlaethyl-2-sllaoorpholine or 1,3-diethylamlnoaethyl-tetramethyl-15 disiloxane.

Nitrogen-containing bases, e.g. tetraalkylaaaonlua hydroxides, allcall aetal hydroxide, e.g. sodium hydroxide, alkali aetal phenolates, e.g. sodium pl^enolate and alkali metal alcoholates, e.g. sodlua aethylate, may also be used 20 as catalysts. Hexahydrotrlazlnes are also suitable catalysts.

Organo-metalllc compounds may also be used as catalysts according to the invention, in particular organo-tln compounds.

The organo-tln compounds are preferably tln(ll) salts of carboxylic acids, e.g. tln(ll) acetate, tln(ll) octoate, 25 tln(ll) ethylhexoate and tin(ll) laurate, and the dialkyl tin salts of carboxylic acids, e.g. dlbutyl tin diacetate, dlbutyl tin dilaurate, dlbutyl tin aaleate or dloctyl tin diacetate.

Other examples of catalysts which aay be used according 30 to the invention and details concerning their action may be found in Kunststoff-Handbuch, Voluae VII, published by Vieweg and HOchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. - 48 - 4027 1 on pages 9b to 102.

The catalysts are generally used In a quantity of froa 0.001 to 10 %f by weight, based on the quantity of isocyanate. 5 Surface act'lve additives, e.g. emulslfiers and foaa stabilisers may also be used according to the present invention. Suitable eaulsiflers include, e.g. the sodium salts of ricinoleic sulphonates or of fatty acids or salts of fatty acids with amines, e.g. oleic acid diethylaaine or stearic 10 acid diethanolaalne. Alkali metal or ammonium salts of sulphonic acids, e.g. dodecylbenzenesulphonie acid or din-aphthylmethane disulphonic acid, or of fatty acids, e.g. ricinoleic acid, or of polymeric fatty acids may also be included as surface active additives. 15 The foam stabilizers used are mainly water-soluble polyether siloxanes. These compounds generally have a polydimethylsiloxane group attached to a copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this kind have been described e.g. m U.S. Patent Specification No. 20 2,764,565.

Negative catalysts, e.g. substances which are acidic In reaction, e.g. hydrochloric acid or organic acid halides; known cell regulators, e.g. paraffins or fatty alcohols or dimethylpolysiloxanes; pigments or dyes; known flame 25 retarding agents, e.g. tris-chloroethylphosphate or ammonium phosphate and polyphosphate; stabilizers against ageing and weathering; plastlcizers; fungicides and bactericides; and fillers, e.g. barium sulphate, kleselguhr, carbon black or whiting may also be used according to the Invention. 30 Further examples of surface active additives, foam stabilizers, cell regulators, negative catalysts, stabilizers, flame retarding substances, plastlcizers, dyes, fillers and - 49 - 40271 fungicidal.and bacteriocidal substances which say be used according to the invention and details concerning their iimo and mode of action may be found in Kunststoff-Handbuch, Volume VI, published by Vieweg and HOchtlen, Carl-Ilanser-5 Verlag, Munich 196<>, e.g. on pages 103 to 113.

Suitable known water-in-oil emulslfiers may be used to improve the emulsiflability of the aqueous alkali metal silicate solution to form a water-in-oil emulsion. Suitable emulslfiers of this kind include, e.g. ethoxylated novolaks 10 as described e.g. 'in German Offenlegungsschrift No. 2,130,448, ethoxylated and, optionally, hydrogenated castor oil, acrylamide copolymers, hydroxyethyl cellulose, partially saponified polyvinyl acetute and polyvinyl alconol.

The formation of the emulsion is also promoted by 15 including a proportion of polyesters which contain hydrophilic groups, e.g. hydrophilic ether segments or cationic or anionic centres.

Metals salts of saturated and unsaturated monocarboxylic and dicarboxylic acids, in particular salts of the elements 20 of Groups I, I la and III of the Periodic Table and also Zn, Ti and Fe salts are suitable specific emulslfiers which at the same time have good bonding effect. Ca, Mg and Ha salts of aliphatic and aromatic dicarboxylic and dlsulphonic acids are particularly suitable, e.g. calcium phthalate. 25 These products also have the effect of Increasing the mechanical strength.

Commercial silanes, as well as isocyanate-modifled silanes and silicones, may be used both as emulsifier9 and to improve the bond between the organic and inorganic phase. 30 The mixing of the organic and inorganic components may give rise to ol1-ln-water, (0/W), emulsions or water-in-oil, (w/0), emulsions. Mixed types may also be formed in the critical region. The emulsions - 50 - 40271 prepared are preferably W/0 emulsions.

It is possible, by suitable choice of eaulsiflers, to obtain a continuous organic phase even If the systea contains up to 90 % of inorganic component. Particularly suitable 5 eaulsiflers are those with a comb structure of the type which have been proposed, for example, for producing water-filled polyester resin foaas.

Coabinations of polyesters, isocyanates, vinyl coapounds are prepolyaers as described in German Offenlegungsschrift 10 No. 2,062,826 may be used to obtain thixotroplc effects which aay be desirable in special cases, e.g. for grouting coo-positions.

The conventional thixotroplc agents are also suitable,for exanple inory;»ni.c thixotropic agents, e.g. "Aerosil", ("Trade Mark) 15 or organic agents which contain acid amide or urethane groups, or cyclohexylaaldes of higher fatty acids, ( German Auslegeschrift Nos. 1,182,816 and 1,217,611 and Belgian Patent Specification No. 693,580).

To improve the fire characteristics and increase the 20 heat resistance and long tera resistance to fire, additional flaae retarding agents aay be added, e.g. halogen- or phosphorus-containing coapounds. These products, however, should only be used in such an amount that the number of acid equivalents, (calculated as IIC1, HBr or ttjPO^) will be less 25 than the number of basic equivalents of the alkali metal silicate solution. Formation of acidic fumes and smoke is thereby prevented.

Suitable flame retarding agents include e.g., tris-chloro-ethylphosphate, tris-(dibromo-propyl)-phosphate, 30 octachloro-dihydroxydiphenyl, bromomethylated alkylphenols, and resitols.

Polymer compositions of the kind described in U.S. - 51 - 4 0 271 Patent Specification No. 3,663,463 are also suitable for use as flaae resistant resins.

Particularly preferred flame retarding agents are dlcyandiaaide, urea, melamlne, guanldine, carbohydrates, e.g. starch, mannltol, sorbitol, saccharose, mannose and galactose, particularly in combination with phosphoric acid.

Additional flaae retarding agents which may be used are, in particular, those which have a direct extinguishing effect in the presence of heat or sparks either because they undergo endotheraic decomposition, thereby uslng-up heat, and/or because they evolve incombustible gases which have an extinguishing effect and/or because they have a coking effect. Examples Include: carbonates of alkaline earth aetals and/or of zinc, sodium carbonate, sodium bicarbonate as well as hydrates of Inorganic compounds which are difficult to decoapose in the heat, e.g. aluminium hydroxides, zinc borate hydrate, condensates of urea, dlcyan-diamide, melamlne and phosphoric acids, oxalates, hydrazides, antimony oxide, antlaony trichloride, (also acts as hardener for the Inorganic phase), and borates.

To provide an additional water-binding effect in systems which have a higher water content, water-soluble vinyl monomers, e.g. acrylamide, hydroxyalkylacrylates or metha-crylates, and vinylsulphonic acid may be added in combination with water-insoluble initiators.

The production of the inorganic-organic plastics in accordance with the present invention is simple. The organic components are merely mixed homogeneously with the aqueous alkali metal silicate solution, whereupon, in most cases, hardening of the mixture begins at once. The mixtures are typical finely divided emulsions or sols. They are not - 52 - 40371 optically olear but are, la most oases, opaque or allky-white. The subsequent xerosol appears to be perforaed in thea.

The mixture of coaponents is not stable. The so-called 5 "pot life" during which the aixtures remain in a workable condition depends aainly on the chealcal nature of the reactive groups of the prepolyaer mixture and oo the total quantity of silicate hardener liberated,as well as on the concentration of the silicate solution. The pot life varies 10 from 0.2 seconds to 2 hours. Pot lives of up to several hours or even several days aay he reached in prepolyaers which contain only a small quantity of NCO groups. A pot life of from 30 seconds to 20 minutes Is preferred.

Thus, even very large shaped products, e.g. pieces 15 weighing 200 kg or even 1,000 kg may easily be produced.In this way.

A particular advantage of the present invention lies, among other things, in the controlled way in which the pot life or working time aay be influenced. If the organic component Is exclusively an lsocyanate, then in most cases, 20 the pot life Is short, e.g. from 1 to 5 minutes. In such cases, when the reaction starts, the reaction velocity increases very rapidly due to the evolution of heat and therefore, in many cases, the final hardening is completed only one or two minutes after the onset of the reaction. 25 This means that the time available for working is extremely short. For numerous purposes, e.g. casting shaped products or filling cavities, this is a great advantage. On the other hand, for other purposes, such rapid hardening is a disadvantage. 30 Thus, in many cases, it Is desirable to keep the reaction at the stage of a thickened, but still plastlo or thermoplastic, intermediate stage, e.g. in the case of compositions used - 53 - 10 2 7 1 for filling Joints or cracks, for modelling work or for carrying out forming work on plate goods, for embossing, deep drawing or blowing up, in short wherever rapid industrial manufacture in several stages is desired.

This present invention provides solutions to problems for the most varied requirements of working consistencies and hardening conditions.

Thus, for example, it is possible to prepare liquid mixtures which, after a certain pot life, undergo an increase in viscosity changing to a viscous, easily workable state In which hardening only proceeds slowly, but may be completed rapidly by the application of heat. Furthermore, the liquid preliminary products may be used to produce plastic masses which remain in a workable state for a practically indefinite period and may, when required, be hardened either by adding a hardening catalyst or by heating.

These systems which may be hardened stepwise may also be produced from masked isocyanates, in which case the final hardening of the isocyanates may afford advantages, for example in improving the bond strength.

The mixing of the components may be carried out In one or more stages. Moreover, one of the components, for example, may be in a microencapsulated form. For example, amine hardeners for any epoxy resins added should not be present in their free state together with unmasked isocyanates because they would then react with the isocyanates and no longer be available for epoxide hardening.

One or more of the organic components of the mixture may also be in the form of a concentrated aqueous dispersion. In particular, this may be advantageous if the resin i component has a high viscosity, e.g. in the case of epoxy resins. - 54 - 40271 According to one particular eabodiaent of the present invention, highly viscous starting aaterials are used and the organic and inorganic components are nixed together by kneading, and the reactive nass is shaped while it is still plastic and then left to harden. 5 The organic component nay be prepared froa an isocyanate prepolyaer, optionally Basked, an unsaturated polyester resin and aonoaers which have a low vapour pressure, e.g. aalelc acid esters or acrylates, while the inorganic coaponent contains water glass and hardener. 10 Both conponents aay contain a high proportion of filler.

The hardening aay proceed spontaneously or, alternatively, it nay be initiated by heating if a longer pot life is required.

In sone cases, e.g. for producing surface coatings, 15 thin-walled parts or grouting conpositions, it is generally not necessary to use an additional silicate hardener. The sane applies to conblnations which contain condensable resins together with acidic hardening catalysts.

However, additional hardeners are frequently required 20 if the conblnations also contain unsaturated polyester resins.

Suitable hardeners for this purpose are generally conpounds which liberate acids in the presence of aqueous alkalies, e.g. esters, anhydrides and halides of carboxylic acids, carbonic acids or sulphonic acids and also the conventional 25 inorganic hardeners, e.g. alunlniun, magnesium or zinc salts and annonlum salts, e.g. ammonium phosphate. Exanples of organic hardening catalysts and data concerning their % hardening velocities nay be found e.g. in German Offenlegungsschrift No. 2,214,609; 2,210,837; 2,228,359; 2,164,957; 30 2,153,352 and 2,165,912.

The conpositions according to the present invention are suitable for producing conpact materials and also foans - 55 - 10271 linvimt densities of from 2.0 to O.OG6, preferably from 1.4 to 0,02, as well as various coating materials. Compact shaped products and materials particularly suitable for 1 underground and surface engineering and furniture 5 construction as well as high density foams are produced mainly with the addition of water binding fillers and also, optionally, inert fillers. The quantity of filler, in particular inorganic filler, may far exceed the quantity of the three essential components of the Invention 10 and may amount e.g. to from 200 to 900 * of this quantity. lnccrtain cases, e.g. where the compositions according to the invention are used as binders for gravel, stone chips or coarse sand, the proportion of "filler" may be as much as 30,000*. 15 For producing foams by the process according to the invention, it is advisable to add blowing agents even if the NCO prepolymers are capable of producing carbon dioxide. These blowing agents are inert liquids boiling in the range of from -25 to 50 "C and preferably from -15 to 'iO°C. The 20 blowing agents are preferably insoluble in the silicate solution.

Suitable blowing agents are in particular alkanes, alkenes, halogenated alkanes and alkenes and dialkylethers. They may be saturated or unsaturated C^ or C^ hydrocarbons, 25 e.g. lsobutylene, butadiene, lsoprene, butane, pentane, petroleum ether, or halogenated saturated or unsaturated hydrocarbons, e.g. chloromethyl, methylene chloride, . fluorotrlchloromethane, difluorodichloromethane, trifluoro-chloromethane, chloroethane, vinyl chloride and Vinylidene 30 chloride. The most suitable have been found to be trichlorofluoromethane, vinyl chloride and C,f hydrocarbons, e.g. butane. - 56 - 40271 The blowing agents are used In quantities of from 0 to 50 % by weight, preferably froa 2 to 30 *, by weight, based on the reaction alxture.

The foaas aay^ of course, also be produced with the 5 aid of inert gases, in particular air, for exaaple one of the two reactants may first be foaaed with air and then aixed with the other components. Alternatively, a foam aay be formed directly,e.g. by aixlng the coaponents with air under pressure, this foam aay then be shaped 10 and hardened at the same time.

To produce the foam, the reaction mixture may also be saturated with gas under pressure so that the gas expands when the pressure is released.

Suitable gases Include e.g. carbon dioxide or a 15 mixture of carbon dioxide and air, e.g. at a pressure of from 20 to 150 atmospheres, the carbon dioxide at the same time serving to harden the Inorganic phase.

If phenol resins or amine resins, which harden under acidic conditions are present, the blowing agents aay be 20 replaced by alneral salts which produce gases under the action of the calalyst, for exaaple calcium carbonate, dolomite, barium carbonate and sodium bicarbonate.

Hydrogen peroxide is also a suitable blowing agent, (see German Offenlegunqsschrift No. 2,227,688), optionally in 25 combination with reducing agents, (German Offenlegungsschrift No. 2,227,640). Combinations of hydrazines with a-halocar-boxyllc acid esters are also suitable.

Other substances, e.g. the emulslfiers, activators and foam stabilizers, conventionally used for producing 30 polyurethane foams, amy also be added but they are generally not necessary. The addition of silanes, polysiloxanes, polyether polysiloxanes or sllyl-modlfled Isocyanates may - 57 - 4 0 2 71 reinforce the interaction between the two phases.

Particularly high quality plastics are obtained by the process according to the invention if hardening is carried out at temperatures above 80°C and in particular 5 from 100 to 200°C.

In many cases, so much heat is liberated, even without external heating,that the water contained in the mixture starts to evaporate and temperatures above 150°C are easily reached in the interior of the foam blocks. 10 It appears that under such conditions there are particularly pronounced interactions between the inorganic and organic polymer and an exceptionally intimate bond Is formed between them so that the resulting materials are n<H only rock hard but at the same time highly elastic and 15 therefore exceptionally resistant to shock and breakage.

If the heat evolved in the reaction between the components is not sufficient, mixing may easily be carried out at elevated temperatures, for example from 40 to 100°C. In certain cases, mixing may even be carried out above 100°C, 20 at temperatures up to approximately 150°C and also under pressure so that when the material leaves the apparatus the pressure is released and foaming sets In.

If the foam is produced at elevated temperatures one may, of course, also adil higher boiling blowing agents, 25 e.g. hexane, dichloroethane, trichloroethane, carbon tetrachloride or light petrol. On the other hand, the water contained in the mixture may take over the function of blowing agent. Fine metal powders, e.g. calcium, magnesium, aluminium or zinc powders, may also act as blowing "50 agents by evolving hydrogen if the. water glass is sufficiently alkaline. At the same time, these powders have a strengthening effect on the product. - 58 - 40271 Basically, the production of foams in accordance with the invention ia carried out by mixing the described reactants, simultaneously or in several stages, in an Intermittently or continously operating mixing apparatus 5 and then allowing the resulting mixture to foam up and solidify, usually outside the mixing apparatus In moulds or on suitable supports. The required reaction temperature of from 0 to 200°C and preferably from 50 to 160°C may be obtained either by preheating one or more of the reactants 10 prior to mixing or by heating the mixing apparatus itself.

Alternatively, the reaction mixture may be heated after the components have been mixed.' Any combination of these or other methods may, of course, be employed for adjusting the reaction temperature. In most cases, sufficient t 15 heat is evolved during the reaction to. enable the reaction temperature to rise above 100°C after onset of the reaction or foaming.

In the case of any given formulation, the properties of the resulting foams, e.g. their density In the moist 20 state, depend, to some extent, on the details of the mixing process, e.g. the form and speed of the stirrer, the form of the mixing chamber and the reaction temperature employed at the onset of foaming. This density may vary from 0.01 to 1.3 g/cm^ and, in most cases, densities of from 0.1 to 25 0.8 g/cm' are obtained in the moist, fresh foam. The dried foams may have closed or open cells but are, in most cases, substantially open-celled with densities of from 0.02 to 1.1 g/cm\ Concrete-type foams with a high filler content have densities of from 0.1 to 2.0 g/cm'. 30 The characteristics of the reaction mixtures give rise i to many possible uses and fields of application for the present invention, some of which will be outlined below. - 59 - 40271 For example, the possibility of either leaving the water In the hardened mixture as a desirable constituent of the foam and even, if desired, of protecting the foam against loss of water by suitable coating or laminating or, 5 . alternatively, or partly or completely removing the water by suitable drying processes, e.g. drying in a drying cabinet, or by the application of hot air, Hi, ultrasound or high frequency (HF), which may be selected from case to case according to the individual requirements of the 10 product.

The reaction mixture containing the blowing agent may, e.g. be painted on to hot or cold supports or supports exposed to IK or I1F waves or, after passing through the mixing apparatus, the reaction mixture may be sprayed onto 15 supports of these types by means of compressed air or, alternatively, by the air-less spraying process. Subsequently, the mixture foams up and hardens on these supports to form a filling or insulating or moisture proofing coating. The foaming reaction mixture may be forced, cast or injection 20 moulded into cold or heated relief moulds, solid moulds or hollow moulds and left to harden in these moulds at room temperature or temperatures up to 200°C, optionally under pressure, optionally employing a method of centrifugal casting. When carrying out this operation, inorganic and/or ~5 organic reinforcing elements may be Included, e.g. metal wires, fibres, fleeces, foams, woven fabrics and skeletons. For example, this may be carried out by the fibre mat impregnation process or by processes in which the reaction mixtures and reinforcing fibres are together applied to the 30 mould, e.g. by means of a spray apparatus.

Moulded articles obtainable in this way may be used as building elements, e.g. in tbe form of foamed or unfoamed - 60 - 40371 sandwich elements whioh may be used directly or in a laminated form with, e.g. metal, glass or plastics. In these sandwich elements, the advantageous fire characteristics in the moist or dry state are an advantage* S On the other hand, the products may he used as hollow articles, e.g. as containers for keeping goods moist or cool, as filter materials or exchangers, as catalyst carriers or carriers of other active substances, as decoration elements, furniture components and cavity to fillings. They may also be used as heavy duty lubricants and coolants or carriers of such substances, e*g« in metal extrusion presses. The products may also be considered for use in the field of furniture construction And model building and for the manufacture of moulds for metal casting. 15 According to one preferred procedure, the foaming process is made to proceed simultaneously with hardening, for example by preparing the reaction mixture in a mixing chamber and at the same time adding the volatile blowing agents, e.g. dichlorodlfluoromethane, trichlorofluoromethane, 2u butane, lsobutylene or vinyl chloride, so that, if the mixing temperature is suitably chosen, the reaction mixture foams up as it leaves the mixing chamber due to evaporation of the blowing agent and at the same time, hardens due to the action of the hardener so that the resulting foam, which i'y may still contain emulslfiers and foam stabilizers and other additives, is fixed. Furthermore, the reaction mixture, which initially is a low viscosity liquid, may be blown up into a foam by introducing gases, e.g. air,methane, CF„ or ai inert gas, optionally under pressure, and Introducing jo the foam into the required mould where it is left to harden.

Alternatively, the silicate- or prepolymer-ionomer solution, which may contain foam stabilizers, e.g. wetting agents, foam-forming agents, emulslfiers and possibly other - 61 - 40271 ' organld or 'Inorganic filler* or diluents, aay be gasified to convert it into a foaa which may then be aixed with the other component and optionally a hardener in a mixing apparatus and then left to harden, 5 According to a preferred aethod, a solution of the prepolyaers in liquid blowing agents is aixed with the aqueous alkali aetal silicate solution, optionally aftar first heating the alkali aetal silicate solution, and the aJxture is then left to harden under conditions of foaming. 10 Instead of blowing agents, finely divided Inorganic e.g. or organic hellow particles/ beads of expanded plastics and straw, may be used for producing the foaas.

The foams which aay be obtained In this way nay be used as Insulating materials, cavity fillings, packaging 13 materials and as building materials. These foams which may, if desired, first be compacted or tempered, optionally under pressure, have good solvent resistance and advantageous fire characteristics. These products may be used as lightweight building elements in the form of sandwiches, 20 e.g. with metal covering layers e.g. in house building and in the construction of motor vehicles and aircraft.

The reaction mixtures may also be foamed and hardened while in the form of droplets, e.g. as dispersions in petroleum hydrocarbons, or they aay be foamed and hardened 25 while under free fall to produce foam beads.

If desired, organic and/or inorganic particles which have been foamed or are capable of foaming, e.g. particles of expanded clay, expanded glass, wood, popcorn, cork, hollow beads made of plastics, e.g. vinyl chloride poly-30 mers, polyethylene, styrene polymers or foam particles thereof or, for example, polysulphone, polyepoxide, polyurethane, urea-formaldehyde, phenol-formaldehyde or polylmide - b 'J. - 40271 polymers may be Incorporated in the foaming reaction mixtures while they are still fluid orf alternatively, heaps of these V particles may be permeated with the foaming reaction mixtures to produce insulating materials which have excellent fire characteristics.

If a blowing agent, e.g. an optionally halogenated hydrocarbon, wh{.ch is capable of evaporating and forming a gas under a given temperature, is added at this temperature to a mixture of aqueous silicate solutions and hardeners, optionally containing inorganic and/or organic additives, then the resulting mixture, which is initially liquid, may be used, not only for producing uniform foams or foams containing other foamed or unfoamed fillers, but also for permeating fleeces, webs, meshes, constructional elements and other permeable structures of foamed material with foam to produce composite foams which have special properties, e.g. advantageous fire characteristics, which may, in some cases, be used directly as constructional elements in bouse building and the manufacture of furniture, motor vehicles and aircraft.

The foams according to the lnention may be added in a crumbly form to soil, optionally mixed with fertilizers and plant protective agents, to Improve the agricultural consistency of the soil. Foams which have a high water content may be used as substrate for the propagation of young shoots, seedlings and plants or for holding cut flowers. Dy spraying these mixtures on terrain which is impassable or too loose, such as dunes or marshes, the terrain may be effectively solidified so that it may be walked over within a short time and is protected against erosion.

The present reaction mixtures also have an application in the case of fire or disaster where they may be sprayed on articles which are required to be protected. The water contained in the mixtures cannot run down the surface of the protected article and cannot evaporate rapidly, so that a very effective protection against fire, heat or radiation is obtained since the hardened mixture cannot beoome heated to temperatures much above 100°C so long as it still contains water, and it will also absorb IR or nuclear radiation.

Since the mixtures may easily be sprayed, they may be used for forming effective protective walls and layers in mines, both in the case of accident and also for routine work, for example by spraying them on fabrics or other surfaces or grids or also simply on walls. A particularly important characteristic for this purpose is that the mixtures harden rapidly.

Similarly, the foaming mixtures may also be used, e.g. in underground and surface engineering and road building, for erecting walls and igloos and for sealing, filling, plastering, priming, insulating and decorating and as coatings, flooring compositions and linings. Their use as adbesives or mortar or casting compounds, optionally with inorganic or organic fillers, may also be considered.

Since the hardened foams according to the present invention are highly porous after drying, they are suitable for use as drying agents because they are then able to absorb water again. On the other hand, they may be charged with active substances or used as catalyst carriers, filters or absorbents.

Auxiliary agents which may be added to the reaction mixture or introduced subsequently, e.g. emulsifiers, detergent raw materials, dispersing agents, wetting agents, perfumes or substances which render the mixture hydrophobic. - 64 - 4027 I enable tbe properties of the f oaths to be nod if led as desired in the aqueous or dry state.

Furthermore, the f6ams>, in their aqueous or dried or inpregnated state, may subsequently 'be lacquered, 5 netallised, coated, laminated, galvanized, vapour treated, bonded or flocked. Forming operations may be carried out on the shaped articles in their aqueous or dried state, for exaaple by sawing, cutting, drilling, planing, polishing or other such processes. 10 The shaped products, with or without filler, may be further modified in their properties by,e.g. thermal after-treatments, oxidation processes, heat pressing, sintering processes or surface melting or other sealing or compacting processes. 15 The moulds may suitably be made of inorganic and/or organic foamed or unfoamed material such as metals, e.g.: iron, nickel, refined steel or lacquered or "TefIonised" aluminium, or porcelain, glass, gypsum, cement, wood or plastics, e.g. PVC, polyethylene, epoxy resins, poly-20 urethanes, ABS and polycarbonate.

The foams obtained according to the invention may be surface dried or, in cases where they are substantially permeable structures, e.g. high grade open-celled foams or porous materials, they may also be dried by centrifuglng, 25 vacuum treatment, or by passing dehydrating liquids or gases through them, (optionally with heating), e.g. methanol, ethanol, acetone, dioxane, benzene, chloroform air, COg and steam.

The moist or dried shaped products may also be 30 subsequently rinsed or impregnated with aqueous or non aqueous acidic, neutral or basic liquids or gases, e.g. hydrochloric acid, phosphoric acid, formic acid, acetic - 05 - 4 0 27 1 acid, amaonla, amines, organic or Inorganic salt solutions, lacquer solutions, solutions of monomers which lmv«* lio«n polymer I»«mI or nrn vol to !>«» polymer »nr«<l, ilyi* noIiiIIoiim, I vmii I •/.« 11 on Imllis or Nolullons of catalysts or catalyst 5 precursors or perfumes.

• Tho ct«i|JOsi le plastics or tlie prcstmt invention, arc jxirticularly suitable for use as constructional material because they have a high tensile strength and compression resistance and are tough and stiff and yet elastic and have a high 10 dimensional stability to heat and good flame resistance.

Thus, for example, high quality lightweight building panels may be produced either by cutting or sawing contin-usouly foamed blocks or by foaming such panels in moulds, optionally under pressure. This moulding process is also 1*3 particularly suitable for producing complicated shapes.

Uy suitably controlling the operating conditions it is also possible to obtain moulded products which have a dense outer skin.

The process according to the invention is also 20 particularly suitable when ^n situ foaming on the actual building site is required. Any hollow moulds normally produced by shuttering in forms may be obtained by casting and foaming. Also, cavities, joints and cracks may conveniently be filled with the reaction mixture, a very 25 firm bond being obtained between the materials which are Joined together in this way. The reaction mixtures may also be used to produce insulating indoor plasters simply by spraying.

In many cases, the materials obtained may be used 30 instead of wood or hard fibreboard. They may be worked by sawing, grinding, planing, nailing, drilling and cutting and are therefore versatile in their uses and possible - 66 - 40271 applications.

Very brittle llghtwolght founts which may be obtained e.g. with a very high silicate content or by using combinations with brittle organo-polymers, may easily be crushed 5 In suitable apparatus to form dust—fine powders which may be used for many purposes as organo-modlfled silicic acid nilers. The organo-modificatlon ensures good surface interaction with polymers and, in many cases, also ensures a certain surface thermoplasticity which enables high 10 quality moulding materials to be obtained with which topo— chemical surface reactions may be carried out by the addition of cross-linking agents.

For many use purposes, additional fillers in the fern of particulate or pulverulent materials are incorporated in 15 the mixtures of prepolymer-ionomers and alkali metal or ammonium silicates.

The fillers, used, e.g. in the form of powder, granulate, wire, fibres, dumb-bell shaped particles, cry-stallites, spirals rods, beads, hollow beads, foam particles, 20 fleeces, woven or knitted fabrics, tapes or foil pieces, may be solid inorganic or organic substances, for example dolomite, chalk, clay, asbestos, basic silicic acids, sand, talc, iron oxide, aluminium oxide and hydroxides, alkali metal silicates, zeolites, mixed silicates, calcium 25 silicates, calcium sulphates, alumlnosilicates, cements, basalt wool or powder, glass fibres, carbon fibres, graphite, carbon black, Al, Fe, Cu and Ag powder, polybdenum sulphide, steel wool, bronze or copper fabrics, silicon powder, feldspar, quartz sand, hollow metal silicate beads, expanded clay 30 particles, hollow glass beads, glass powder, lava and pumice particles, wood chips, wood meal, cork, cotton, straw, popcorn, coke and particles of filled or unfilled, foamed - 67 - or unfoaaed, stretched or unstretched organic polymers.

Among the numerous suitable organic polymers which may be used, e.g. as powders, granulates, foam particles, beads, hollow beads, particles which can he foamed but have not yet been foamed, fibres, tapes, woven and non-woven webs, the following are mentioned as examples, polystyrene, polyethylene, polypropylene, polyacrylonitrile, polybutadlene, polyisoprene, polytetrafluoroethylene, aliphatic and aromatic polyesters, melaaine-urea resins or phenol resins, polyacetal resins, polyepoxides, polyhydantoins, polyureas, polyethers, polyurethanes, polimides, poly-amides, polysulphones, polycarbonates and, of course, any copolymers thereof.

Inert fillers may also be produced in situ in the reaction mixture by adding the required reactants for producing them either simultaneously or successively to the reaction mixture.

The preferred fillers are chalk, talc, dolomite, gypsum, clay, anhydrite, quartz sand, highly disperse silica, content , lime, qlass, carbon and the conventional plastics and rubber waste.

In principle, the composite materials according to the invention may be filled with considerable quantities of fillers without losing their advantageous properties.

Fillers which are particularly preferred and which have a marked reinforcing effect are the organic or inorganic water binding, (hydraulic), aggregates, e.g. hydraulic cements, synthetic anhydrite, gypsum and slaked lime.

Suitable hydraulic cements are, in particular, Cortland cement, qutck setting cement, high furnace cement, low calcined cement, sulphate-resistant cement, brick cement, natural cement, lime cement, gypsum cement, Puzzolana - 68 - 40271 cement and calcium sulphate cement.

For producing hard materials, the water binding aggregates are preferably used in a quantity which is sufficient to bind from 40 to 100 % of the water Introduced with the j silicate solution. In particular, the quantity of water binding aggregates may amount to froa 50 to 200 $ hy weight, of the quantity of "total mixture", (sum of 3 major components).

Additional inert aggregates which may also be added are, jq in particular, sand, quartz sand, brick dust and short-cut glass fibres which penetrate both organio and inorganic phases and thereby reinforce the bond.

Furthermore, particles, e.g. expanded clay, expanded glass, pumice powder, slag, gravel and coarse stone chips 15 may be permeated with foam.

Fillers as well as inert aggregates may be steeped, impregnated or sprayed with one of the liquid components of the mixture before the mixing process proper, e.g. in order to Improve the bond between the components or the fluidity. 20 The binding of the water Introduced with the alkali metal silicate solution by the hydraulic binders, e.g. cement, lime or anhydrite, is of major importance for tbe behaviour of the materials in the case of fire. On exposure to heat, the bound water is slowly given off endotherm-25 lcally and thereby provides a powerful fire inhibiting effect.

Accordingly, it may be desirable to keep the water enclosed in the composite material even In the absence of the hydraulic binders or water binding filler#. For this 30 purpose, the continuous organic phase should be as hydrophobic and lmperaeable to water vapour as possible.

In addition, water-binding substances, e.g. glycol, - 69 - 40271 dlglycol, glycerol, sorbitol, methyl glucosldes, sucrose and cellulose and starch ethers, may be added to the silicate phase.

Tbe production of above-described foam concrete 5 is generally carried out by mixing the reactants in one or more stages in an intermittently or continuously operated mixing apparatus and then leaving the resulting mixture to foam up and solidify, in most cases outside the mixing apparatus in moulds or on suitable supports, Tbe required 10 reaction temperature of from 0 to 200°C, preferably from 50 to lbO°C, may be obtained either by preheating one or more of the reactants prior to mixing or by heating the mixing apparatus itself, or alternatively, heating the reaction mixture after it has been mixed. Combinations 15 of these or other methods are, of oourse, also suitable for adjusting the required reaction temperature. In most cases, sufficient heat Is evolved during the reaction to enable the reaction temperature to rise above 100°C after onset of the reaction or foaming.

JO When mixing the components, the water binding aggre- , i l any, is »|onrr;illy lirst ncklod to the organic component or to the alkali metal silicate or both to the organic component and to the alkali metal silicate, but there is no disadvantage in adding the water binding aggregate subse-25 quently to a mixture of the organic components and the silicate or vice versa.

Auxiliary substances, e.g. blowing agents, catalysts, stabilizers, emulslfiers, flame retarding agents and inert fillers, may be added to the various reactants, but the 30 blowing agent is preferably added to the organic component and the catalyst to the alkali metal or ammonium silicate.

Mixing the reactants is preferably carried out at - 70 - 40271 room temperature,but nay well be carried out at any temperature from —20 to +80°C.

A foam concrete having optimum usa properties, in particular high strength, elasticity, dimensional stability 5 to heat and advantageous fire resisting properties, is obtained if I ho proporl ion of .kjucouu .ilkali metal or ammonium silicate solution is from 20 to 70 jt, by weight, based on the total mixture, the porportlon of organic components is from 10 to 50 *, by weight, based on the total mixture, and 10 the proportion of water binding aggregates is from 20 to 70 by weight, based on the total mixture. These ranges are therefore preferred. Uy "total mixture" is meant the sum of components of the mixture, including the water-binding aggregate. 15 Mixtures of 30 to bO Jt, by weight, based on the total mixture, of aquc-ius alkali metal silicate solution; from 10 to 35 by weight, based on the total mixture, of organic polyiso-20 cyanate; and from 30 to 60 *, by weight, based on the total mixture, of water-binding aggregates are preferred both because they result in surprising pro— 25 pertles and because they are highly economical.

From the above proportions it will be seen that tbe proportions of polyisocyanate, alkali metal silicate and water-binding filler used for producing foam concretes are not critical. This is particularly advantageous for 30 continuous methods of production because it is then not necessary to measure the quantities very accurately. It is therefore possible to use sturdy delivery devices, e.g. - 71 - 027 1 gear wheel pumps or Monho pumps or screws.

For any given formulation, the properties of foam concrete obtained, e.g. its density, depend to some extent on the details of the mixing process, e.g. the form and speed ol the stirrer, the form of the mixing chamber and the selected reaction temperature when foaming is started. The density may vary from 100 to 1300 kg/m^, but gross densities of from 200 to 800 kg/m' are preferred.

The foam concrete may have an open-cell or closed-cell structure but, in most cases, it is largely open-celled and has densities of from 100 to 600 kg/m' and compression o strengths of from 5 to 150 kp/cm .

The foamable reaction mixture may also be poured into colli or heated moulds and left to harden in these moulds, which may be relief moulds or solid or hollow moulds, at room temperature or temperatures of up to 200°C, optionally under pressure.

Moulded products with dense marginal zones and completely non-cellular, smooth surfaces may be obtained by using the technique of foaming in the mould. When using this technique, inorganic and/or organic reinforcing elements, e.g. metal wires, fibres, fleeces, foams, fabrics and skeletons, may be Included. Moulded foam concrete products obtainable in this way may be used directly as building elements or in the form of sandwich elements which may be used directly or subsequently laminated with, e.g. metal, glass or plastics.

These materials are distinguished not only by their advantageous fire characteristics, but also by the fact that if organic or inorganic materials, e.g. paints, gypsum, putty or sand compounds, are subsequently applied to them, they adhere very firmly to the foam concrete. - 72 - 4027 1 The foam concrete according to the present invention may, of course, also be made up into blocks which may subsequently be divided into panels or lightweight building bricks, e.g. by sawing, and if desired they may be laminated in the above-5 described manner, or otherwise provided with covering layers by various techniques. It is preferred, however, to produce the required shaped products directly.

The compression strengths of tbe materials obtained according to the Invention depend to a large extent on the lu proportions in which the starting components are mixed and the resulting density, e.g. densities of from 200 to 600 kg/m' and compression strengths of from 10 to 100 kp/cm^ are obtained by using a mixture of approximately equal parts of polyisocyanate, alkali metal silicate and water-r> binding filler and at the same time using approximately 5 by weight, (based on the total quantity), of low boiling blowing agent.

Important advantages of the present invention are the short mixing times and the rapid hardening. When mixing is 20 carried out discontinuously, it is completed within from 15 seconds to 5 minutes, and hardening generally takes less than 30 minutes.

These advantages may be exploited in production processes thus acheivlng short dwelling times and hence quick operating cycles.

According to the present invention, foam concrete having excellent fire resistance is obtained if the sum of inorganic constituents is more than 30 Jt, by weight, and preferably more than 50 %, by weight, of the total mixture. M The ease with which a foam concrete according to the present invention may be worked affords important advantages, for example the concrete may easily be sawn, screwed, nailed, drilled and cut, and therefore has wide possibilities of - 73 - <1027 1 application.

Depending on Its composition and structure, the foam concrete according to the invention may be capable of absorbing water and/or water vapour or it may afford a considerable resistance to diffusion of water and/or water vapour.

The foam concrete according to the invention opens up new possibilities in underground and surface engineering and In the production of prefabricated parts and elements.

Various possible applications include, e.g. the production of wall elements In prefabricated building, lost shutterlngs, roller shutters, window benches, railway and underground sleepers, kerbstones, stairs, the filling of Joint9 with foam and the back filling of ceramic tiles with foam.

The foam concrete may also be used advantageously for binding gravel or marble chips. Decorative panels may be obtained In this way which may be used, for example as facade elements.

Compact materials are produced. In particular, as moulded articles which may be obtained by casting, reactive injection moulding or extrusion.

It is also possible, especially If the lsocyanate content Is low, to mix the components to produce a pasty, workable reaction mixture which may be used for impregnating fibrous webs, for example of glass, and which may then be further worked in a conventional manner and hardened by the application of heat.

The following Examples illustrate the invention: Preparation of the starting motcrials (I) The dinuclear content of the crude phosgenation product of an aniline-formaldehyde condensate Is distilled off until the distillation residue has a viscosity of 400 cl' 40271 at 25°C. The resulting product is sulphonated to a sulphur content of 1 jt by passing sulphur triozide over it with stirring. Viscosity: 1300 cP at 25°C.

(II) 370 g ethylene glycol, 630 g diethylene glycol, 5 27<>0 g 3,4,5,6,7,7-hexachloro-3,6-endomethylene-l,2,3,6- tetrahydrophthalic acid and 496 g maleic acid are heated to 170°C under a stream of carbon dioxide, 143 g water being distilled off in the process. The resulting polyester is poured out at 120°C onto a metal sheet where it 10 solidifies to a hard, brittle resin having an acid number 46. A 63 % solution of this resin in styrene is prepared.

(III) 730 g adiplc acid, 980 g maleic acid anhydride, 740 g phthalic acid anhydride and 1250 g ethylene glycol are slowly heated together at 150°C. When 225 g water 15 have distilled off, 75 g N,N-bis-(hydroxyethyl)-anillne are added. Condensation is continued for 7 hours at from 155 to 250°C, a further 155 g water being split off. Condensation is then continued at 190°C and under 15 Torr for 3 hours until the acid number is 5. After the 20 addition of 2.5 g hydroquinone, 1400 g styrene are stirred in at 110°C. Viscosity at 25°C: 5800 cP.

(IV) 188 g, (2 mol), phenol, 116 g (3.8 mol), paraformaldehyde, 48.7 g, (0.6 mol), formaldehyde (37 % aqueous solution, pll 7) and 12.6 g (0.04 mol), barium hydroxide 25 octahydrate are together stirred at from 40 to 45°C for 2 hours. An exothermic reaction takes place. Condensation is then completed at from 60 to 65°C, (2 hours), and from 70 to 75°C, (li hours).

(V) 188 g; (2 mol), phenol, 325 g (4 mol), formaldehyde 30 (37 % solution pll 7) and 4 g, (0.1 mol), sodium hydroxide are gently heated, with stirring, at from 40 to 45°C for 2 hours and then at from 60 to 65°C for 2 hours. 24 g, - 75 - 4027 I (O.'i aol), urea are added to the condensation solution which is then stirred for a further 2| hours at froa 70 to 75°C.

(VI) 215.6 g, (2.2-aol), concentrated sulphurlo acid is added dropwise to 188 g, (2 aol), phenol over a period 5 of 20 ainutes at 70°C, the temperature rising to 81°C.

Heating is continued at froa 120 to 127°C for 40 ainutes after the exotheraic reaction has died down. The reaction aixture is then left to cool. 98 g, (1.2 aol), 37 % aqueous formaldehyde solution are added over a period 10 of 1 hour and the mixture la stirred for 2} hours and diluted with 80 al water. Viscosity (25°C) '»(>3 cP.

(VII) 50 % solution in styrene, (prepared at 100°C), ot a distillation residue obtained froa the distillation of commercial tolylene diisocyanate. NCO content 15 11.8 %, viscosity at 25°C: 5030 cl'.

(VIII) As (VII), but using a 60 $ solution in styrene. NCO content 14.6 %. Viscosity at 25°C: 100,000 cP.

(IX) As (VII), prepared in the presence of hydroqulnone at 20°C„ Viscosity at 25°C: 68 cP. - 76 - 40271 Component II Example 1 100 g (1) 50 g (III) ) Component I 3 g 50 $ benzoyl peroxide 5 150 g hk $ sodium water glass (Na20:Si02=l:l) 3 g trie thylamina The components are stirred together for 15 seconds and the emulsion is then poured out on to a concrete 10 slab. A solid coating has formed after 2 minutes.

Example 2 The procedure is the same as in Example 1, but using the following composition of component I 40 g (I) 15 120 g (III) 1 g 50 % benzoyl peroxide.

The viscosity rises steeply within 2 minuses after the emulsion has been poured out. The plastic mass may be formed and hardened in the course of 10 minutes. 20 Kxample 3 100 g (I) 50 g (III) 80 g styrene j Component 1 k g 50 % benzoyl peroxide 25 150 g kh % sodium water glass 3 g triethylamine The components are stirred together for 15 seconds and the emulsion Is then poured Into a mould. A hard panel is obtained after 90 seconds. 30 Component II - 77 - 40271 10 15 20 25 30 Component 1 Component 11 Kxample 4 150 g (I) 30 g (IJ I) 2 g 50 % benzoylperoxide 'i0 g fluorotrichloromethane 150 g h>i * sodium water glass 4 g triethylamine 0.5 g N (50 jt aqueous solution of the sodium salt of a, sulpbochlorlnated paraffin mixture The components are mixed and the emulsion Is poured into a paper mould. The mixture foams up to form a very hard and compression resistant foam with coarse pores and a unit weight of 700.

Kxample 5 80 g (I) <>0 g (11) 0.5 g bls-(hydroxyethyl)-anlline 4 g 50 % benzoyl peroxide 40 g trlchlorofluoromethane 150 g 44 * sodium water glass 0.5 g triethylamine 0.1 g N (see Kxample 4) Foaming carried out as in Kxample 4.

Stirring time 13 seconds.

Onset of foaming after 38 seconds Knd of foaming after 56 seconds 100°C 120 seconds.

A very hard, compression resistant foam with coarse pores and a unit weight of 300 is obtained.

Component I Component II - 78 - Component I Component II 40271 Example 6 50 g (I) 100 g (II) 50 g Portland cement 5 0.5 g bis-(hydroxyethyl)-aniline 2 g 50 % benzoyl peroxide 150 g 44 % sodlua water glass 0.5 g triethylamine 0.1 g N (see Kxample 4) 10 Mixing the components results in a thick emulsion which rapidly hardens when poured out.

Kxample 7 150 g (i), 20 g (IV), 10 g (VI) and 30 g chloro- benzene are mixed and stirred simultaneously into 100 g of 15 a solution of 80 g 54 % sodium water glass (Na 0:Si0o=l:2) 2 i and 20 g water, (stirring time 10 seconds). The mixture becomes thick within 10 minutes but remains in deforaable plastic state for over 24 hours. It is suitable for use, e.g. as putty, grouting composition and joint filling 20 composition. After 2 days, the mass has become hard and brittle at room temperature. It is preferable to reheat the mass after it has been shaped,(e.g. one hour at 100°C). The product then obtained Is very hard and at the same time tough.. 25 Example 8 150 g (I), 20 g (IV), 10 g (VI) and 30 g trichloro-fluoromethane are mixed for 7 seconds with 102 g of an aqueous solution defined below and tbe resulting emulsion is poured into a paper mould. It foams after .40 seconds 30 and reaches its maximum expansion after 108 seconds, and has a final temperature of 60'C after 5 minutes. The foamed mass remains in a plastic, deformable state for approximately - 79 - 2't hours and may be hardened nt the desired timo by heating. Composition of the aqueous solution: 80 g 54 % 8odium water glass (Na20:S102s 1:2), 20 g water, 1 g triethylamine, and 1 g of a polyethersiloxane foam stabilizer (IC1 "Siloocell 7200").

Examples 9-18 In the following series of experiments, the constituents of component 1 are first mixed separately and so are tbe constituents of component II. The two components are then mixed with the aid of high speed stirrer and poured into moulds. In the presence of trichlorofluoromethane, foams are obtained and in other cases homogeneous moulded products or panels are obtained. - 8O - voz- i cd Zxer.ple Nos, 'Pi (nil ; ityrsne l:iS-0X0wfcj*l-a-.ilir.e benzoyl peroxide crici'.ioro-fluorosethans 9 90 60 C.5 4 40 10 90 60 C.5 4 4C 11 90 60 0,5 4 40 12 90 60 0.5 4 40 13 100 50 ICC v.5 4 40 14 50 100 40 C.5 4 15 50 100 fO 100 0.5 4 1o 50 100 40 200 C.5 4 .17 150 60 100 0.5 4 18 150 1C0 o.5 4 ft o t9 -I Component II Example ' Water No. glass Trietbyl- E Tempe- Stirring Foam rises amine rature time after (se cond) Max, rises after Temper* (seconds) ature Remarks O M •J 10 11 12 13 14 15 16 17 18 150 150 150 150 150 150 150 150 150 150 0.5 0.5 1.5 2.5 1.5 1.0 1.0 1.0 1.0 1.0 0.1 25' 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 25° 25° 25° 25° 60° 40° 50° 25° 0.1 50< 15 seconds 20 seconds 15 seconds 20 seconds 15 seconds 15 seconos 15 seconds 15 seconds 10 seconds 15 seconds 110 75 67 42 50 123 100 79 46 65 S7° 62 = 68° 66° 100° 74° 72° 73° 33° 80° coarse pores, bard, compression resistant very coarse pores, bard medium sized pores, bard, compression resistant fine pores, bard, compression resistant fine pores, very hard, compression resistant solidification after 35 seconds, bard solidification after 60 seconds, hard very bard, concrete-like still deforaable after 11 minutes, hardens at 60° bard 40271 to Kxanples 19-22 Kor comparison, casting compounds are prepared by mixing a poly Isocyanato, an unsaturated polyes'ter resin and combInaLions of the two materials with water glasx and I then leaving the mixtures to harden. The advantageous working properties of the conblnations according to the Invention are then very clear.

Kxanple mo. 19 20 21 22 (1) 100 g 10 g 5 g - (II) 100 g 100 g 100 g His—(2—hydroxy- — ethylaniline) 0.5 g 0.5 g 0.5 g 50 % benzoyl — peroxide 2 g 2 g 2 g 'i'i % sodium silicate solution 100 g (Na20:Si02=l:2) 100 g 100 g 100 g 2» no longer fluid after 30" no longer plastically deforaable after deforaabi-11 ty 1* not given 2 • 25» 23 min 3' 2h 2hours 38' not plastically deforaable smeary, increasingly elastic mass - 83 -

Claims (11)

4027 1 C LA I MS: - I

1. A process for producing an inorganic-organic plastic which comprises reacting: (a) from 20 to 85%, by weight, based on the total 3 reaction mixture, of aqueous alkali metal or ammonium silicate solution; (b) from 5 to 70%, by weight, based on the total reaction mixture, of an organic isocyanate; and (c) frcm lO to 75%, by weight, based on the total reaction 1" mixture, of: (i) polymerisable compounds which contain double bonds, in combination with free radical initiators or cross-linking agents; and/or (ii) phenol resin condensates and/or precondensates, 15 optionally in combination with acidic hardeners; and/or (iii)urea rosin or melamino rosin condensates and/or precondensates, optionally in combination with acidic hardeners; and/or 20 (iv) diepoxides or polyepoxides, in combination with diamines or polyamines.

2. A process as claimed in claim 1 in which the said reaction mixture also contains other compounds which are reactive with isocyanates and/or inert aggregates. 25

3. A process as claimed in claim 1 or claim 2 in which at least one of the constituents of component (b) and/or (c) has at least one ionic and/or hydrophilic group.

4. A process as claimed in any one of claims 1 to 3 in which a mixture of component (b) with component (c) is jo mixed with component (a). 40271

5. A process as claimed in claim 4 in which the said mixture of component (b) with component (c) comprises a solution of commercial distillation residues of aromatic poly— isocyanaces in styrene.

6. A process as claimed in any of claims 1 to 5 in which the said reaction mixture also comprises xinsaturated polyester resins.

7. A process as claimed in claim 1 substantially as herein described.

8. A process as claimed in claim 1 substantially as herein described with reference to any one of the Examples.

9. Inorganic-organic plastics when produced by a process as claimed in any of claims 1 to 8.

10. Materials or articles derived from inorganic-organic plastics as claimed in claim 9.

11. Materials or articles as claimed in claim 10 substantially as herein described. F. R. KELLY & CO. AGENTS FOR THE APPLICANTS. - 85 -