GB1571184A

GB1571184A - Stable heterogeneous dispersions of ionic polyisocyanate-polyaddition products

Info

Publication number: GB1571184A
Application number: GB4674576A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1975-11-12
Filing date: 1976-11-10
Publication date: 1980-07-09
Also published as: ES453242A1; JPS5815492B2; NL7612546A; FR2331580B1; BR7607551A; AU499976B2; IT1066769B; SE7612593L; JPS5260898A; DD129138A5; AT353010B; ATA833776A; FR2331580A1; AU1956276A

Description

(54) STABLE HETEROGENEOUS DISPERSIONS OF IONIC POLYISOCYANATE-POLYADDITION PRODUCTS (71) We, BAYER AKTIENGESELL SCHAFT, a body corporate organised under the Laws of Germany of 509 Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a process for the preparation of finely divided, stable and relatively low viscosity heterogeneous dispersions of polyisocyanate polyaddition products in compounds having hydroxyl groups, and the use of such dispersions as starting components for the production of polyurethane resins.

Non-ionic diisocyanate polyaddition products dispersed in polyethers or polyesters are already known. According to the teaching of German Auslegeschrift No.

1,168,075, diisocyanates are reacted with bifunctional primary alcohols in a dispersing medium consisting of a polyether or polyester (molecular weight 500 to 3000) containing at least two (exclusively secondary) hydroxyl groups in the molecule.

According to German Auslegeschrift No.

1,260,142, compounds containing isocyanate and amino groups are made to undergo a polyaddition reaction in situ in a polypropylene glycol ether used as dispersing agent. Non-ionic dispersions of polyurethanes, polyureas or polyhydrazodicarbonamides in polyvalent, higher molecular weight hydroxyl compounds obtained by the above mentioned processes are recommended as thickeners for the textile or dye industry because of their high viscosities even at low solids contents.

Thus a 10% (or 200/o) dispersion of polyhydrazodicarbonamide in a polypropylene glycol ether obtained according to German Auslegeschrift No.

1,260,142, for example, has a viscosity of over 10,000 (or 200,000) cP at 250C. This amounts to more than 10 (or 200) times the viscosity of the pure dispersing agent. When attempts are made to prepare a 400/, dispersion, the reaction mixture solidifies before polyaddition has been completed.

The high viscosities which occur at even relatively low solids contents seriously restrict the possibilities of using the products because, in many fields of application, they cannot be dosed with the aid of the usual dosing apparatus. For producing polyurethane foams, for example, a purpose for which such dispersions could be used according to an earlier proposal by the present applicants, (German Offenlegungsschrift No. 2423984), the viscosities of the starting materials must be below 2500 cP when conventional high pressure machines are employed.

It has now been found that stable heterogeneous ionic dispersions having the desired low viscosity can be obtained by reacting polyisocyanates with compounds having salt groups or groups capable of salt formation and, optionally, other, non-ionic chain lengthening agents "in situ" in dispersing agents consisting of compounds containing hydroxyl groups if this reaction is carried out either continuously in continuous flow mixers, in the presence of up to 30 /" by weight of water, preferably more than one percent by weight of water, based on the total quantity of reaction mixture or, and this is preferred because of the simpler dosing and mixing technique and the in many cases easier removal of heat of reaction, in simple stirrer apparatus (batchwise reaction in vessels) in the presence of a larger quantity of water, up to 50V by weight, preferably more than 50/, by weight, based on the total quantity of reaction mixture.

The latter is particularly surprising for the following reasons: A water content of 10, 15 or 20 S by weight (based on the total quantity of polyether and water), for example, increases the viscosity of a polyalkylene ether glycol at 25"C to 4, 8 and 50 times, respectively, the original value (3500, 7300 and over 50,000 cP). If the water content is further increased, the solution or emulsion originally obtained in many cases separates into two phases. Both the high increase in viscosity and phase separation inevitably led experts to assume that the addition of water would be unsuitable for the commercial production of low viscosity polyisocyanate polyaddition products in compounds containing hydroxyl groups, particularly since the water might, in addition, interfere chemically with the isocyanate polyaddition reaction.

The present invention thus relates to stable heterogeneous dispersions having a solids content of from 1 to 70 ,4 by weight of a polyisocyanate polyaddition product containing ionic groups, in a hydroxyl, containing compound having a molecular weight of 62 to 16,000 and to a process for the in situ preparation of such stable heterogeneous dispersions of polyisocyan ate polyaddition products in hydroxyl containing compounds as external continuous phase by the reaction of 1) an organic polyisocyanate with 2) a compound having primary and/or secondary amino groups and/or primary hydroxyl groups in 3) a compound having at least two hydroxyl groups, which hydroxyl groups are less reactive towards isocyanates than the isocyanate reactive groups of compound 2 compound 3) containing secondary hydroxyl groups in cases where compounds 2) contain primary hydroxyl groups, in which process at least one of the components 1) or 2) contains ionic groups or groups which may be converted into ionic groups after the reaction of components 1 and 2, the components being reacted in the presence of up to 50V by weight of water, preferably more than 1% by weight, more preferably from 5 to 50% and most preferably 10 to 250/, by weight of water, based on the total quantity of reaction mixture, the water being subsequently removed in known manner if desired.

According to the invention, the compounds used as component 2) are preferably polyamines and/or hydrazines and/or hydrazides.

In another embodiment of the process according to the invention, the reactants 1) and/or 2) may in part consist of monoisocyanates and/or primary or secondary monoamines and/or monohydrazides for the purpose of adjusting the product to a particular molecular weight. Alkanolamines may also be used in the polyaddition reaction for the same purpose. In this way, ionic polyurea or polyhydrazodicarbonamide particles containing reactive groups are also obtained.

Although emulsifying and dispersion stabilizing substances such as polyethers which contain amino, semicarbazide or hydrazide groups in addition to one or two hydroxyl groups may be added if desired, the addition of such compounds is generally not necessary since emulsifying groups are already built into the ionic polyaddition compounds.

The stable heterogeneous dispersions according to the invention are in particular dispersing of polyurethanes, polyureas or polyhydrazodicarbonamides in external continuous phases consisting of compounds having at least two hydroxyl groups.

The invention further relates to the use of the heterogeneous ionic dispersions according to the invention as starting components for the production of polyurethane resins, in particular foams.

The compounds used as component 3 in accordance with the present invention, that is the continuous, external phase, are alcohols containing 2 to 8, preferably 2 to 6, most preferably 2 to 4 primary and/or secondary hydroxyl groups and having a molecular weight of from 62 to 16,000, preferably 62 to 12,000 and most preferably 106 to 8000.

These include, for example, both low molecular weight alcohols or glycols having a molecular weight of from 62 to 400 which may also contain ether, thioether or ester bonds and polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester amides having molecular weights of more than 400, such as those known per se for the production of polyurethanes.

Suitable low molecular weight compounds to be used- as continuous external phase include diols or triols of the kind conventionally used as chain lengthening agents or cross-linking agents in polyurethane chemistry, e.g. propylene glycol - (1,2) and -(1,3); butylene glycol (1,4) and -(2,3); hexanediol-(1,6): octanediol-(1,8): neopentyl glycol; cyclohexane dimethanol (1,4 - bis hydroxymethylcyclohexane), 2 - methyl - 1,3 - propanediol; glycerol; trimethylolpropane; hexanetriol - (1,2,6); butanetriol (1,2,4) or trimethylolethane and, particularly, glycols having a hydrophilic character, e.g. ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol, and polyethylene glycols having a molecular weight of up to 400. In addition, however, compounds such as dipropylene glycol, polypropylene glycols having a molecular weight of up to 400, dibutylene glycol, polybutylene glycols having a molecular weight of up to 400, thiodiglycol and castor oil may also be used as external continuous phase according to the invention, also ester diols of the general formulae HO-CH2)x-CO-O-(CH2)y-OH and HOCH2)rnCO-O-(CH2)v-OH HO(CH2)xOCORCOO (CH2)xOH in which R represents an alkylene or arylene group preferably having from 1 to 10, more preferably 2 to 6 carbon atoms; x=2 to 6 and y=3 to 5, e.g. 5 - hydroxybutyl - E - hydroxy - caproic acid ester; w - hydroxy- hexyl - y - hydroxybutyric acid ester; adipic acid - bis - (p - hydroxy- ethyl) ester and terephthalic acid - bis - (p hydroxyethyl)- ester; as well as diol urethanes of the general formula HO(CH2)xOCHNHR' NHCOO(CH2)xOH in which R' represents an alkylene, cycloalkylene or arylene group having from 2 to 15, preferably 2 to 6, carbon atoms and x represents an integer of from 2 to 6, e.g.

1,6 - hexamethylene - bis - (p - hydroxy- ethylurethane) or 4,4' - diphenylmethane bis - (5 - hydroxybutylurethane); or also diolureas of the general formula

in which R" represents an alkylene, cycloalkylene or arylene group having from 2 to 15, preferably 2 to 9 carbon atoms, R"'=H or CH3 and x=2 or 3, e.g. 4,4' - diphenylmethane - bis - ( - hydroxyethylureas) or the compound

Particularly suitable among the dihydric and trihydric low molecular weight alcohols are those which, either alone or as mixtures or with the addition of higher molecular weight alcohols, are liquid at temperatures below 50 C.

Higher molecular weight hydroxyl polyesters which are suitable as external continuous phases include e.g. reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added, and polybasic, preferably dibasic carboxylic acids. Instead of free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or polycarboxylic acid esters of lower alcohols or mixtures thereof may be used for preparing the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and they may be substituted, e.g. by halogen atoms, and/or unsaturated. The following are mentioned as examples: Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethylterephthalate and bis - glycol terephthalate. Suitable polyhydric alcohols include e.g.. ethylene glycol, propylene glycol-(1,2) and -(2,3), butylene glycol-(1,4) and -(2,3), hexanediol-(1,6), octanediol (1,8), neopentyl glycol, cyclohexane dimethanol (1,4 - bis - hydroxymethyl cyclohexane), 2 - methyl - 1,3 propanediol, glycerol, trimethylolpropane, hexanetriol - (1,2,6), butanetriol - (1,2,4), trimethylolethane, triethyleneglycol, tetracethyleneglycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols.

The polyesters may also contain a proportion of carboxyl end groups.

Polyesters of lactones, e.g. E-caprolactam, or hydroxycarboxylic acids, e.g. - hydroxycaproic acid, may also be used.

The higher molecular weight polyethers preferably used as external continuous phase according to the invention are obtained in known manner by reaction of the starting compounds which contain reactive hydrogen atoms with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or with any mixtures of these alkylene oxides. In many cases it is preferred to use polyethers which contain predominantly primary hydroxyl groups.

Suitable starting compounds containing reactive hydrogen atoms include e.g. water, methanol, ethanol, ethylene glycol, propylene glycol-(1,2) or -(1,3), butylene glycol-(1,4) or -(2,3), hexanediol-(1,6),octane diol-(1,8), neopentyl glycol, 1,4bis - hydroxymethylcyclohexane, 2 methyl - 1,3 - propanediol, glycerol, trimethylolpropane, hexane triol (1,2,6), butanetriol - (1,2,4), trimethylolethane, pentaerythritol, mannitol, sorbitol, methylglycoside, sucrose, phenol, isononylphenol, resorcinol, hydroquinone, 1,2,2- or 1,1,3 - tris (hydroxyphenyl) - ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethylenediamine, diethylenetriamine, ethanolamine, diethanolamine, triethanolamine, aniline, phenylenediamine, 2,4 - and 2,6 - diaminotoluene and polyphenyl- polymethylene - polyamines of the kind obtained by aniline formaldehyde condensation. Resinous material such as phenol and resol resins may also be used as starting materials.

Polyethers modified by vinyl polymers are also suitable for the process according to the invention. Products of this kind may be obtained by polymerising e.g. styrene and acrylonitrile in the presence of polyethers (US.-Patent Nos. 3,383,351, 3,304,273, 3,523,095, 3,110,695, German Patent No.

1,152,536).

Among the polythioethers should be particularly mentioned the condensation products obtained from thiodiglycol on its own and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. The products obtained are either polythio mixed ethers or polythioether esters or polythioether ester amides, depending on the cocomponents.

Suitable polyacetals include e.g. the compounds which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4' - dioxethoxy - diphenyldimethylmethane, hexanediol and formaldehyde, Polyacetals suitable for the purpose of the invention may also be prepared by the polymerisation of cyclic acetals.

Suitable polycarbonates containing hydroxyl groups include those known per se such as the products obtained from the reaction of diols such as propanediol-(1,3), butanediol-(1,4) and/or hexanediol-(1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. diphenylcarbonate, or phosgene.

Suitable polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines or mixtures thereof.

Mixtures of the above mentioned high and low molecular weight compounds may of course also be used as external continuous phase according to the invention, as already mentioned above.

The compounds which are preferred for use as external continuous phase according to the invention are those which are free from any labile groups, e.g. ester groups, liable to be destroyed by hydrolysis or aminolysis in the process according to the invention. Unstable compounds of this kind are preferably added to the finished dispersion only after completion of the polyaddition reaction.

The hydroxyl compounds and mixtures thereof used as external continuous phase according to the invention should be chosen so that when mixed with the water which may be added according to the invention and with any hydroxyl compounds or, preferably, amino compounds and optionally inert solvents, they are liquid at the reaction temperature, i.e. in the form of solutions or emulsions. Their viscosity at the reaction temperature should generally be below 20,000 cP and preferably below 5000 cP so that conventional stirrer amd mixing apparatus can be employed.

If inert solvents are to be used, they should preferably distil off as azeotropic mixtures with water, for example benzene and toluene.

The following compounds or mixtures thereof may be used in the process according to the invention as components 1) and 2) which contain at least one hydrogen atom reactive with isocyanate groups or at least one isocyanate group and at least one ionic group or group capable of salt formation: I) Compounds containing basic amino groups capable of being neutralised with aqueous acids or tertiary amino groups capable of being quaternised: a) Alcohols, in particular hydroxyalkylated aliphatic, cycloaliphatic aromatic and heterocyclic secondary amines, e.g.

N,N - dimethylethanolamine, N,N diethylethanolamine, N,N - dibutyl ethanolamine, 1- dimethylamino propanol - (2), N,N - methyl - - hydroxyethylaniline, N,N - methyl 13 - hydroxypropylaniline, N,N ethyl - - hydroxyethylaniline N,N butyl - ,B- hydroxyethylaniline, N hydroxyethylpiperidine, N - hydroxy ethylmorpholine, a - hydroxy ethylpyridine and y - hydroxy ethylquinoline.

b) diols and triols, in particular dihydroxyalkylated aliphatic, cycloaliphatic, aromatic and heterocyclic primary amines, e.g. N methyl - diethanolamine, N - butyl diethanolamine, N - oleyl diethanolamine, N - cyclohexyl diethanolamine, N - methyl - disso propanolamine, N - cyclohexyl diisopropanolamine, N,N dioxyethylaniline, N,N - dioxyethyl m - toluidine, N,N - dioxyethyl - p toluidine, N,N - dioxy - propyl naphthylamine, N,N - tetraoxyethyl a - aminopyridine, dihydroxy ethylpiperazine, polyethoxylated butyl diethanol- amine, polypropoxylated methyl diethanolamine (molecular weight 1000), polypropoxylated methyl diethanolamine (molecular weight 2000), polyesters having tertiary amino groups, tri - [2 - hydroxypropyl - (1)] amine, N,N - di - n - (2,3 - dihydroxy propyl) - aniline, N,N' - dimethyl N,N' - bis - hydroxyethylhydrazine and N,N' - dimethyl - N,N' - bis hydroxypropyl - ethylenediamine.

c) Amino alcohols, e.g. products of addition of alkylene oxide and acrylo nitrile to primary amines, which addition products are obtained by hydrogenation, for example N methyl - N - (3 - aminopropyl) ethanolamine, N - cyclohexyl - N (3 - aminopropyl) - propanol - (2) amine, N,N - bis - (3 - aminopropyl) - ethanolamine and N - 3 aminopropyl - diethanolamine.

d) Amines, e.g. N,N - dimethylhydrazine; N,N - dimethyl - ethylenediamine; 1 - di - ethylamino - 4 - amino - pentane; a - aminopyridine; 3 - amino - N - ethylcarbazole; N,N - dimethyl propylene - diamine; N aminopropyl - piperidine; N - amino propyl - morpholine; N - amino - propyl - ethyleneimine and 1,3 - bis piperidino - 2 - aminopropane.

e) Diamines, triamines, amides, in particular those obtained by hydrogenation of products of addition of acrylonitrile to primary or disecondary amines, e.g. bis - (3 aminopropyl) - methylamine, bis - (3 aminopropyl) - cyclohexylamine, bis (3 - aminopropyl) - aniline, bis - (3 aminopropyl) - toluidine, diaminocarbazole, bis (aminopropoxyethyl) - butylamine, tris - (aminopropyl) - amine, or N,N' bis - carbonamidopropyl hexamethylendiamine, and the compounds obtained by the addition of acrylamide to diamine or diols.

II) Compounds containing halogen atoms which are capable of quarternizing reactions or the corresponding esters of strong acids: 2 - Chloroethanol, 2 - bromoethanol, 4 chlorobutanol, 3 - bromopropanol, fi chloroethylamine, 6 - chlorohexylamine, ethanolamine - sulphuric acid ester, N,N bis - hydroxyethyl - N' - m - ehloromethyl- phenylurea, N - hydroxyethyl - N' - chlorohexylurea, glycerol amino - chloroethyl - urethane, chloroacetyl - ethylenediamine, bromoacetyl- dipropylene - triamine, tri ehloroaeetyl - triethylenetetramine, glycerol a - bromohydrin, polypropoxylated glycerol - cr- chlorohydrin, polyesters containing aliphatically bound halogen or 1,3 - diehloropropanol - 2.

The following are mentioned as corresponding isocyanates: Chlorohexylisocyanate, m - ehlorophenyl - isocyanate, p - ehloro - phenylisocyanate, bis - chloromethyl- diphenylmethane diisocyanate 2,4- diisocyanato - benzyl chloride 2,6 - dissocyanato - benzyl chloride, N - (4 - methyl - 3 isocyanatophenyl) - p - bromoethyl urethane.

III) Compounds containing carboxylic acid or hydroxyl groups capable of salt formation: a) Hydroxy and mercapto carboxylic acids: Glycollic acid, thioglycollic acid, lactic acid, tri - chlorolactic acid, malic acid, dihydroxymaleic acid, dihydroxyfumaric acid, tartaric acid, dihydroxytartaric acid, mucic acid, saccharic acid, citric acid, glyceroboric acid, pentaerythrito - boric acid, mannitoboric acid, salicylic acid 2,6 dihydroxybenzoic acid, protocatechuic acid, a - resorcylic acid, p - resorcylic acid, hydroquinone - 2,5 dicarboxylic acid, 4 hydroxyisophthalic acid, 4,6 dihydroxyisophthalic acid, hydroxyterephthalic acid, 5,6,7,8 tetra - hydronaphthol - (2) carboxylic acid - (3), 1 hydroxynaphthoic acid-(2), 2,8 dihydroxynaphthoic acid-(3), p- hydroxypropionic acid, m hydroxybenzoic acid, pyrazolone carboxylic acid, uric acid, barbituric acid, resols and other formaldehyde phenol condensation products.

b) Polycarboxylic acids: Sulphodiacetic acid, nitrilotriacetic acid, ethylene diaminotetracetic acid, diglycollic acid, thiodiglycollic acid, methylene - bis thioglycollic acid, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, gallic acid, phthalic acid, tetrachlorophthalic acid, isophthalic acid, terephthalic acid, naphthalene tetracarboxylic acid - (1,4,5,8), o - tolyl - imido diacetic acid, p - naphthylimido diacetic acid, pyridine dicarboxylic acid, dithiodipropionic acid.

c) Aminocarboxylic acids: Oxaluric acid, anilinoacetic acid, 2- hydroxy carbazole - carboxylic acid - (3), glycine, sarcosine, methionine, a - alanine"B - alanine, 6 - aminocaproic acid, 6- benzoyl- amino - 2 chlorocaproic acid, 4 - amino - butyric acid, aspartic acid, glutamic acid, histidine, anthranilic acid, 2 ethylaminobenzoic acid, N- (2 carboxyphenyl) - aminoacetic acid, 2 (3' - amino - benzenesulphonylamino) benzoic acid, 3 - aminobenzoic acid, 4 - aminobenzoic acid, N phenylamino - acetic acid, 3,4 diaminobenzoic acid, 5 aminobenzenedicarboxylic acid, 5 (4' - aminobenzoylamino) - 2 aminobenzoic acid.

d) Hydroxy and carboxy sulphonic acids: 2- Hydroxyethane sulphonic acid, phenolsulphonic acid-(2), phenolsulphonic acid-(3), phenolsulphonic acid-(4), phenoldisulphonic acid-(2,4), sulphoacetic acid, m-sulphobenzoic acid, p-sulphobenzoic acid, benzoic acid - (I) - disulphonic acid - (3,5), 2 chloro - benzoic acid - (I) - sulphonic acid - (4), 2 - hydroxy - benzoic acid (1)- sulphonic acid - (5), naphthol (I) - sulphonic acid, naphthol - (I) - disulphonic acid, 8 - chloronaphthol (1) - disulphonic acid, naphthol - (I) trisulphonic acid, naphthol - (2) sulphonic acid - (1), naphthol - (2) trisulphonic acid acid, 1,7 - di hydroxy - nephthalenesulphonic acid (3), 1,8 - dihydroxy - naphthalene disulphonic acid - (2,4), chromotropic acid, 2 - hydroxynaphthoic acid - (3) sulphonic acid - (6), 2- hydroxy carbazole - sulphonic acid - (7).

e) Aminosulphonic acids: Amidosulphonic acid, hydroxylamine monosulphonic acid, hydrazine disulphonic acid, sulphanilic acid, N- phenylamino methanesulphonic acid 4,6 dichloroaniline - sulphonic acid - (2), phenylene diamine - (1,3) - disulphonic acid - (4,6), N - acetyl naphthyl - amine (I) - sulphonic acid (3), naphthylamine - (1)- sulphonic acid, naphthylamine - (2) - sulphonic acid, naphthylaminedisulphonic acid, naphthylamine - trisulphonic acid, 4,4' - di - (p - aminobenzoyl amino) - diphenylurea- disulphonic acid-(3,3'), phenyl - hydrazine disulphonic acid-(2,5), 2,3 - dimethyl 4 - aminoazo - benzene - disulphonic acid-(4',5), 4' - aminostilbene disulphonic acid - (2,2') - 4 - azo - 4 anisol, carbazole - disulphonic acid - (2,7), taurine, methyltaurine, butyltaurine, 3- amino - benzoic acid - (1) - sulphonic acid - (5), 3 amino - toluene - N- methane sulphonic acid, 6- nitro - 1,3 dimethylbenzene - 4 - sulphamic acid, 4,6 - diaminobenzene - disulphonic acid - (1,3), 2,4 - diaminotoluene sulphonic acid - (5), 4,4' diaminodiphenyl- disulphonic acid (2,2'), 2 - aminophenol - sulphonic acid - (4), 4,4' - diamino - diphenyl ether - sulphonic acid - (2), 2 - amino anisole - N - methanesulphonic acid, 2 - amino - diphenylamine - sulphonic acid.

Salt forming agents for Group I may be inorganic or organic acids or compounds containing reactive halogen atoms or the corresponding esters of strong acids. The following are some examples of such compounds: Hydrochloric acid, nitric acid, hypophosphorous acid, amidosulphonic acid, hydroxylamine monosulphonic acid, formic acid, acetic acid, glycollic acid, lactic acid, chloroacetic acid, ethyl bromoacetate, sorbitoboric acid, methyl chloride, butyl bromide, dimethysulphate, diethylsulphate, benzyl chloride, p toluene - sulphonic acid methyl ester, methyl bromide, ethylene chlorohydrin, ethylene bromohydrin, glycero - a - bromohydrin, ethyl chloroacetate, chloroacetamide, bromoacetamide, dibromoethane, chlorobromobutane, dibromobutane, ethylene oxide, propylene oxide and 2,3 - epoxypropanol.

The compounds of Group II may be quaternised or ternised with tertiary amines or also with sulphides or phosphines to produce quaternary ammonium and phosphonium salts and ternary sulphonium salts.

Examples include trimethylamine, triethylamine, tributylamine, pyridine, triethanolamine, the compounds mentioned under groups I a and I b, dimethylsulphide, diethylsulphide, thiodiglycol thiodiglycollic acid, tri - alkylphosphines, alkylarylphosphines and triarylphosphines.

The agents used to form salts with the compounds of Group III may be inorganic or organic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonia or primary, secondary or tertiary amines. Finally, organic phosphorus compounds may also be used as compounds capable of salt formation. These phosphorus compounds include those basic phosphines which can be built into the molecule, e.g. diethyl - ,B hydroxyethyl phosphine, methyl - bis - fi hydroxyethylphosphine or tris - ss hydroxymethylphosphine and derivatives, e.g. phosphinic acids, phosphonous acids, phosphonic acids and esters of phosphorous and phosphoric acid and their thioanalogues, e.g. bis - (a - hydroxy isopropyl) - phosphinic acid, hydroxyalkane phosphonic acid and phosphoric acid - bis - glycol ester.

According to the invention, it is preferred to use ionogenic components carrying sulphona phenylethylamine, 1 - amino - 3,3,5 - trimethyl - 5- aminomethylcyclohexane, 4,4' - diaminodicyclohexylmethane and propane, 1,4 - diaminocyclohexane, phenylenediamines, naphthylenediamines, condensates of aniline and formaldehyde, tolylenediamines, bis - amino methylbenzenes and derivatives of the above mentioned aromatic amines monoalkylated on one or both nitrogen atoms. The polyamines generally have a molecular weight of from 60 to 10,000, preferably 60 to 3000 and most preferably 60 to 1000. Suitable hydrazines include hydrazine itself and mono - substituted or N,N' - disubstituted hydrazines in which the substituents may be C1 to C5 alkyl groups, cyclohexyl groups or phenyl groups. The hydrazines generally have a molecular weight of from 32 to 500. Hydrazine itself is preferred.

Suitable hydrazides include the hydrazides of dibasic or higher basic carboxylic acids such as carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, esters of hydrazine monocarboxylic acid with dihydric or higher hydric alcohols and phenols such as ethanediol, propanediol (1,2), butanediol- (1,2), -(1,3) and -(1,4), hexanediol, diethyleneglycol, triethyleneglycol, tetraethyleneglycol, dipropyleneglycol, tripropyleneglycol and hydroquinone, and amides of hydrazine monocarboxylic acid (semicarbazides), for example with the above mentioned diamines and polyamines. The hydrazides generally have a molecular weight of from 90 to 10,000, preferably 90 to 3000 and most preferably 90 to 1000.

The amines and hydrazines mentioned above may be used in the form of their dilute aqueous solutions or they may be used as mixtures with the external continuous phase diluted with the required quantity of water.

The starting components 1) used according to the invention also include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described, for example, by W.

Siefken in Justus Liebigs Annalan der Chemie, 562, pages 75 to 136 for example ethylene diisocyanate; 1,4 - tetramethylene diisocyanate; 1,6 - hexamethylene diisocyanate; 1,12 - dodecane diisocyanate; cyclobutane - 1,3 diisocyanate; cyclohexane - 1,3 - and 1,4 - diisocyanate and any mixtures of these isomers; 1 - isocyanato - 3,3,5 - trimethyl 5 - isocyanatomethyl - cyclohexane as described in German Auslegeschrift No.

1,202,785 and US Patent Specification No.

3,401,190; 2,4- and 2,6 - hexahydrotolylene diisocyanate and any mixtures of these isomers; hexahydro- 1,3 and/or -1,4phenylene diisocyanate; perhydro - 2,4'and/or 4,4' - diphenylmethane diisocyanate; 1,3- and 1,4 phenylenediisocyanate; 2,4- and 2,6 tolylene diisocyanate and any mixtures of these isomers; diphenylmethane- 2,4'and/or 4,4' - diisocyanate; naphthylene 1,5 - diisocyanate; triphenylmethane 4,4',4" - triisocyanate; polyphenyl - polymethylene polyisocyanates of the kind which can be obtained by aniline formaldehyde condensation followed by phosgenation and which have been described, for example, in British Patent Specifications No. 874,430 and No. 848,671; m- and p - isoeyanatophenyl - sulphonyl isocyanates according to US Patent Specification No. 3,454,606; perchlorinated aryl polyisocyanates such as those described e.g. in German Auslegeschrift No. 1,157,601 and US Patent Specification No. 3,277,138; polyisocyanates containing carbodiimide groups as described in German Patent Specification No. 1,092,007 and US Patent Specification No. 3,152,162; diisocyanates of the kind described in US Patent Specification No. 3,492,330; polyisocyanates having allophanate groups as described e.g. in British Patent Specification No. 994,890; Belgian Patent Specification No. 761,626 and published Dutch Patent application No. 7,102, 524; polyisocyanates having isocyanurate groups as described e.g. in US Patent Specification No. 3,001,973; German Patent Specifications No. 1,022,789, 1,222,067 and 1,027,394 and German Offenlegungsschriften No. 1,929,034 and No. 2,004,048; polyisocyanates with urethane groups, e.g. as described in Belgian Patent Specification No. 752,261 and US Patent Specification No. 3,394,164; polyisocyanates having acylated urea groups according to German Patent Specification No. 1,230,778; polyisocyanates with biuret groups as described e.g. in German Patent Specification No. 1,101,394; US Patent Specifications No. 3,124,605 and 3,201,372; and British Patent Specification No. 889,050; polyisocyanates prepared by telomerisation reactions as described in US Patent Specification No. 3,654,106; polyisocyanates with ester groups, for example those mentioned in British Patent Specifications No. 965,474 and No.

1,072,956; US Patent Specification No.

3,567,763 and German Patent Specification No. 1,231,688; reaction products of the above mentioned isocyanates with acetals according to German Patent Specification No. 1,072,385 and polyisocyanates containing polymeric fatty acid groups according to US Patent Specification No.

3,455,883.

The distillation residues containing isocyanate groups obtained from the commercial production of isocyanates may also be used, if desired as solutions in one or more of the above mentioned polyisocyanates. Any mixtures of the above mentioned polyisocyanates may also be used.

So-called prepolymers may, of course, also be used as isocyanate components according to the invention, that is to say reaction products of low molecular weight and/or higher molecular weight compounds having hydroxyl and/or,amino groups, e.g.

those of the kind mentioned above, with an excess of the monomeric polyisocyanates described above.

Some or all of the isocyanates or amines, hydrazines or hydrazides used in the process according to the invention may have a functionality higher than 2. It must be regarded as surprising that the reaction according to the invention of such higher functional compounds in external continuous phases which have hydroxyl groups does not result in solid or, at least, very highly viscous reaction products but also gives rise to finely divided, low viscosity heterogeneous dispersions.

The polyaddition products produced by the process according to the invention as dispersions in compounds containing hydroxyl groups may, as already mentioned above, be modified by the addition of a proportion of ionogenic but monofunctional isocyanates, amines, hydrazine derivatives or ammonia to which non-ionogenic compounds may also be added.

Thus, for example, the average molecular weight of polyaddition products can be adjusted as desired by the incorporation of such monofunctional compounds.

Polyureas or polyurea polyhydrazodicarbonamides containing free hydroxyl groups can be obtained by using alkanolamines having primary or secondary amino groups. The introduction of other groups such as ester groups, longer aliphatic groups, tertiary amino groups and active double bonds, can also be achieved by the addition of suitably substituted monoamines, diamines or isocyanates.

Suitable non-ionogenic monofunctional isocyanates include e.g. alkyl isocyanates such as methyl, ethyl, isopropyl, isobutyl, hexyl, lauryl and stearyl isocyanate; chlorohexyl isocyanate: cyclohexyl isocyanate; phenyl isocyanate: tolyl isocyanate; 4 - chlorophenylisocyanate and diisopropylphenylisocyanate.

Suitable non-ionogenic monoamines include e.g. alkylamines and dialkylamines containing C, to C8 alkyl groups; cycioaliphatic amines such as cyclohexylamine and its homologues; aniline and N-alkylanilines and aniline derivatives which are substituted in the benzene ring; alkanolamines such as ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine and dibutanolamine and diamines having a tertiary and a primary or secondary amino groups, e.g. N,N dimethyl - ethylenediamine and N methylpiperazine. Suitable monofunctional hydrazine derivatives and hydrazides include e.g. N,N - dialkylhydrazines, the hydrazides of monocarboxylic acids, hydrazine monocarboxylic acid esters of monofunctional alcohols or phenols, and semicarbazides e.g. methyl, ethyl, propyl, butyl, hexyl, dodecyl, stearyl, phenyl, and cyclohexylsemicarbazide.

The molecular weight of the polyaddition products prepared according to the invention as dispersions in hydroxyl compounds is determined by the proportion by weight of polyamine, hydrazine or hydrazide on the one hand to polyisocyanate and monofunctional compounds, if added, on the other. It is particularly preferred to react approximately equivalent quantities of isocyanates and hydroxyl functional or, preferably, amino functional compounds in the hydroxyl containing external continuous phase. Chain lengthening agents which have primary hydroxyl groups are reacted in an external continuous phase containing exclusively secondary hydroxyl groups. A limited excess of isocyanate may also be used but the products then obtained have a relatively high viscosity, increasing with the amount of isocyanate excess used, since the excess of polyisocyanate reacts with the dispersing agent. Low molecular weight chain lengthening agents such as amine, hydrazine or hydrazide, on the other hand, may be used in large excess without causing an increase in the viscosity; polyaddition products having reactive end groups and a limited molecular weight are obtained in such cases. The equivalent ratio of polyisocyanate to chain lengthening agent is generally kept between 0.50 and 1.50 and preferably between 0.90 and 1.10. It is particularly preferred to use approximately equivalent quantities.

When polyisocyanates are reacted with polyamines or hydrazines or hydrazides in the presence of compounds having hydroxyl groups, the isocyanate groups react very preferentially with the amino groups but a certain proportion of the hydroxyl groups of the external continuous phase also take part in the reaction, depending on the reaction conditions. This reaction gives rise to polyurea and/or polyhydrazodicarbon - amide chain which are chemically linked with the monohydric, or preferably, polyhydric alcohol used as external continuous phase. Such end groups presumably have a dispersing action on the solid particles. The extent to which the hydroxyl groups take part in the polyaddition reaction depends particularly on the reaction temperatures and on the water content. If too large a number of higher molecular weight polyol molecules react with the polyisocyanates, highly viscous dispersions are obtained. This obviously occurs in the process according to German Auslegeschrift No. 1,260,142. On the other hand, if the proportion of polyol molecules taking part in the reaction is too low, that part of the resulting dispersions which is composed of the larger particles is liable to be unstable and undergo sedimentation. The process according to the invention which comprises reaction in a simple stirrer apparatus with reflux condenser when large quantities of water are used or in continuous flow mixers when smaller quantities of water are used, has the surprising effect of making it possible for the proportion of the NCO/OH reaction to be adjusted so that finely divided dispersions having the required low viscosity are obtained, but at the same time, coarser parts of the dispersion are still sufficiently stable so that they will not undergo sedimentation even during prolonged storage at elevated temperatures.

If however, the ionic content is very low, it is advisable to include emulsifying substances in the poly-addition reaction to increase the stability of the dispersion.

These emulsifying substances include e.g.

linear polyethers having an average molecular weight of 300 to 4000 and carrying isocyanate groups or amino or hydrazide groups at both ends of the chain or, preferably, at only one end.

Thus, for example, minor quantities of isocyanate adducts of diols having the following general formula

may be used as emulsifying agents. In the above formula, R represents a divalent group such as can be obtained by removal of the isocyanate groups from a diisocyanate having a molecular weight of from 112 to 1000; X represents oxygen or -NR1,-, R' and R", which may be the same or different, represent monovalent hydrocarbon groups having from 1 to 12 carbon atoms, R"' represents hydrogen or a monovalent hydrocarbon group having from 1 to 8 carbon atoms and n represents an integer of from 4 to 89.

The preparation of such hydrophilic diols has been described, for example, in German Offenlegungsschrift No. 2,314,512.

Modified polyethers acting as external continuous phases which may be used according to the invention include not only those having the above general formula but also, for example, addition products of excess diisocyanates and/or polyisocyanates of the kind mentioned above as examples with monofunctional and/or bifunctional hydroxyl polyethers having an average molecular weight of from 300 to 4000, which may be freed from unreacted free isocyanate by thin layer evaporation. If desired, these isocyanate prepolymers may also be reacted with excess free isocyanate to form allophanate isocyanates. Addition products containing isocyanate end groups may also be converted into polyethers containing amino or semicarbazide and groups by reaction with excess diamines or hydrazine, e.g. according to German Auslegeschrifts No. 1,122,254 or 1,138,200.

Polyethers containing amino end groups, e.g. those prepared by the process according to US Patent Specification No.

3,155,278 or German Auslegeschrift No.

1,215,373 may also be used as dispersing agents according to the invention.

Lastly, hydroxyl polyethers may be reacted with phosgene to convert them into chloroformic acid esters which may then be reacted with excess diamine or hydrazine.

As already mentioned above, polyethers which carry an isocyanate or amino group at only one chain end are preferred as dispersing agents.

The modified polyethers which have a dispersing action are generally only added in quantities of up to about 15% by weight, preferably up to 3% by weight (based on the total quantity of polyol and solid content) to the particularly preferred dispersions according to the invention which have a solids content of about 10 to 60 /n by weight If the dispersions have a higher or lower solids content, a correspondingly larger or smaller quantity of dispersing agent is used.

According to a less preferred variation of the process of the invention, compounds of the type mentioned above having two or more primary hydroxyl groups and a molecular weight of from 62 to 400 may be reacted with polyisocyanates to which primary alcohols may be added to produce polyurethane dispersions. In that case, however, it should be noted that only dispersing agents which contain exclusively secondary hydroxyl groups may be used and they should preferably have a molecular weight of more than 500 in order to ensure selective reaction of the polyisocyanate with the primary hydroxyl compounds.

The quantity of water which, according to the preferred embodiment of the invention, is present during the polyaddition reaction is of decisive importance in determining salt formation, particle. size, particle size distribution and the final viscosity of the dispersion. Several factors must be taken into account simultaneously: The viscosity and hydrophilic or hydro-phobic character of the dispersing agent containing alcoholic groups; the solubility or emulsifiability of the starting components used for the isocyanate polyaddition reaction; the ionic content and solids content of the resulting dispersion and the temperatures employed.

The sequence and method of addition may also be of some influence. With increasing water content, a significant increase in viscosity occurs, particularly if the dispersing agent used is only slightly hydrophilic and the ionic content is low, as already mentioned above by way of example. In all cases it is necessary to ensure that the reaction mixture can be vigorously mixed in the presence of water during the polyaddition reaction and during the subsequent removal of water by distillation. The quantity of water added is less than 50 /a by weight but generally at least about 2% by weight, based on the total quantity of the reaction mixture. The higher the desired solids content of the dispersion, the more water should be added. The optimum quantity of water is that which results in the lowest possible final viscosity of the dispersion prepared according to the invention but which does not require the removal of unnecessarily large quantities of water by distillation. The preferred quantity of water is, in many cases, between 5 and 25% by weight based on the reaction mixture.

When very large quantities of water are used, the ionic group content prevents separation of the phases of the reaction mixture during the polyaddition reaction or solidification during the removal of the water by distillation. It is therefore possible to use a much higher solids content than in the case of non-ionic products. If very hydrophilic alcohols are used, it is also permissible to use small quantities of water, i.e. upwards of about 1% by weight.

For obtaining a very low final viscosity, it is also advantageous to employ a very high reaction temperature from the start of the polyaddition reaction, preferably a temperature close to the boiling point of water.

When using stirrer vessels with reflux condensers, the heat produced in the strongly exothermic isocyanate reaction can easily be removed by boiling under reflux. At the same time, any adducts formed in the gaseous phase above the liquid reaction mixture can be continuously washed into the liquid phase by the water while still in statu nascendi and finely dispersed therein.

According to a special embodiment of the invention the properties of polyurethane resins produced from such dispersions can be further modified in a commerically advantageous manner if, instead of using water in the process according to the invention there is used a corresponding quantity of an aqueous polymer latex, for example an aqueous polyurethane dispersion, or an aqueous solution of an ionic polyurethane or a polymer latex or a dispersion of a polycondensation product. The polymer latex or solution should have a solids content of from 1 to 60% by weight, preferably 5 to 40% by weight, so that the ratio by weight of solids content of the polymer latex to polyaddition product prepared in situ is between 1:99 and 99:1 preferably between 10:90 and 90:10 and most preferably between 25:75 and 75:25.

According to the invention any known aqueous latices of polymer condensates and polyaddition products or mixtures thereof may be used. Aqueous dispersions of polyurethanes and/or polymers are particularly widely applicable.

Numerous processes have become known for the preparation of polyurethane dispersions in water. A summarizing report has been given, for example, by D.

Dieterich and H. Reiff in "Die Angewandte Makromolekulare Chemie" 26 1972 (pages 85-106), by D. Dieterich et al in "Angewandte Chemic", 82 1970 (pages 5363) and by D. Dieterich et al in J. Oil Col.

Chem. Assoc. 1970, 53 (363-379). These reports also give a comprehensive survey of the literature. In practice, the most popular method for preparing aqueous polyurethane dispersions comprises reacting an isocyanate prepolymer dissolved in an organic solvent with a chain lengthening agent. In this process, either the prepolymer or the chain lengthening agent contains ionic groups or groups capable of ion formation. These groups capable of ion formation are converted into ionic groups either during the polyaddition reaction or subsequently. Formation of the aqueous dispersion is carried out at the same time or subsequently by the addition of water and removal of the organic solvent by distillation.

As already mentioned above, both cationic and anionic and non-ionic polyurethane dispersions may be used in the process according to the invention.

Aqueous polyurethane dispersions which give rise to polyurethane foils with elastic properties when dry are preferred for the purpose of the invention, particularly rubbery elastic or, at least, high impact resistant polyurethanes, polyureas or polyhydrazodicarbonamides which have a ball pressure hardness below 1400 kp/cm2 (60 seconds according to DIN 53456) and preferably a Shore hardness D of less than 55 and most preferably a Shore hardness A of less than 98. Dispersions of harder polyurethanes may, of course, be used in individual cases for obtaining foams which have special properties.

As already mentioned above, aqueous polyurethane dispersions suitable for the process according to the invention may be obtained quite generally by including in the preparation of the polyurethanes components which contain ionic groups or groups capable of ion formation and, in addition, at least one isocyanate group or at least one hydrogen atom which is reactive with isocyanate groups. Examples of compounds of this kind, which may be used in the form of mixtures are the ionic and ionogenic components I), II) and III) described above.

Cationic polyurethanes suitable according to the invention may be obtained for example, by the process according to German Auslegeschrift No. 1,270,276, if the starting materials used for synthesising the polyurethane include at least one component having one or more basic tertiary nitrogen atoms and the basic tertiary nitrogen atoms of the polyurethane are reacted with alkylating agents or inorganic or organic acids. It is in principle immaterial in what position of the polyurethane macromolecule the basic nitrogen atoms are situated.

Conversely, polyurethanes having reactive halogen atoms capable of quaternising reactions may be reacted with tertiary amines. Furthermore, cationic polyurethanes may also be prepared by a reaction resulting in a chain lengthening quaternisation, for example by preparing dihalogen urethanes from optionallly higher molecular weight diols and isocyanates having reactive halogen atoms or dissocyanates and halogenated alcohols and reacting these dihalogen urethanes with ditertiary amines. Conversely, ditertiary diaminourethanes may be prepared from compounds having two isocyanate groups and tertiary amino alcohols and these diaminourethanes may then be reacted with reactive dihalogen compounds. The cationic polyurethane mass may, of course, also be prepared from a cationic salt-type starting component, for example a quaternised basic polyether or an isocyanate which contains tertiary nitrogen.

These methods of preparation have been described, for example, in German Auslegeschriften No. 1,184,946; 1,178,586 and 1,179,363; US Patent Specification No.

3,686,108 and Belgian Patent Specifications No. 653,223; 658,026 and 636,799. These documents also mention suitable starting materials for synthesising the salt-type polyurethanes.

The anionic polyurethane (urea) dispersions may also be prepared by known methods. Suitable anionic polyurethanes have been described, for example, in German Auslegeschrift No. 1,237,306 and German Offenlegungsschriften Nos.

1,570,565; 1,720,639 and 1,495,847. It is preferred to use starting compounds which contain carboxyl or sulphonate groups as ionic groups.

The anionic dispersions may also be prepared from polyurethanes having free hydroxyl and/or amino groups by reacting them with aliphatic or aromatic aldehydes and, at the same time or subsequently, with a metal sulphite, metal hydro-sulphite, metal aminocarboxylate or metal aminosulphate. Lastly, polyurethanes having free hydroxyl andlor amino groups may be reacted with cyclic compounds which have from 3 to 7 ring members and contain salt-type groups or groups which are capable of salt formation after ring opening as described in German Auslegeschrift No.

1,237,306. Compounds of this kind include in particular sultones such as 1,3propanesultone, 1,4-butanesultone or 1,8naphthosultone; lactones such as ,B- propiolactone or y-butyrolactone and dicarboxylic acid anhydrides, e.g. succinic acid anhydride.

Suitable cationic or anionic polyurethanes for the process according to the invention may also be prepared via a formaldehyde polycondensation reaction according to German Offenlegungsschrift No. 1,770,068. According to this method higher molecular weight polyisocyanates are reacted with an excess of compounds which have methylol end groups, e.g.

aminoformaldehyde resins or phenol formaldehyde resins, and the resulting reaction product which contains methylol groups is dispersed in water and finally cross-linked by heat treatment with the formation of methylene bridges.

It is also possible, but less desirable, to carry out the process according to the invention using products described in German Offenlegungsschriften No, 1,953,345; 1,953,348 and 1,953,349. These are aqueous dispersions of ionic emulsion polymers prepared by radical emulsion polymerisation of olefinically unsaturated monomers in the presence of cationic or anionic oligourethanes or polyurethanes.

Chemically cross-linked aqueous dispersions of cationic or anionic polyurethanes which tend to sediment but are redispersible may also be used according to the invention.

A detailed description of the preparation of cross-linked ionic polyurethane suspensions may be found, for example, in US Patent No. 3,479,310, Canadian Patent No. 837,174 British Patent No. I,158,088, US Patent No. 3,714,095, US Patent No.

3,622,527, British Patent No. 1,175,339 and US Patent No. 3,756,992.

As already mentioned above, non-ionic, self-emulsifying aqueous polyurethane dispersions may also be used for the process according to the invention in addition to cationic and anionic polyurethane dispersions.

The preparation of non-ionic, emulsifierfree polyurethane dispersions which are suitable for the process according to the invention may be carried out, for example, by the process according to German Offenlegungsschrift No. 2,141,807; 1 Mol of a trifunctional polyether polyol is reacted with 3 mols of a diisocyanate. The resulting adduct, which contains isocyanate groups, is reacted with a mixture of a) a monofunctional low molecular weight alcohol and b) a reaction product of a monofunctional alcohol or monocarboxylic acid and ethylene oxide (molecular weight about 600) to yield a prepolymer containing I mol of the monofunctional polyethylene oxide adduct to about 3000 molecular weight units. This prepolymer is emulsified in water with the aid of a mechanical dispersing device to produce a latex which is subjected to the final polymerisation by reaction with water or some other chain lengthening agent known from polyurethane chemistry. The latices are prepared using such a small quantity of water that the solids content is above 45% by weight and preferably about 50% by weight.

According to earlier proposals by the present applicants in German Offenlegungsschriften No. 2,314,512; 2,314,513 and 2,320,719, self dispersible, non-ionic polyurethane dispersions suitable for the process according to the invention may also be prepared by incorporating polyethylene oxide units into linear polyurethanes as side chain units attached by allophanate or biuret groups.

Suitable polymer latices include, for example, those based on natural or synthetic rubber, styrene-butadiene copolymers, neoprene, styrene acrylonitrile copolymers, polyethylene, chlorosulphonated or chlorinated polyethylene, butadiene - acrylonitrile copolymers, butadiene - methacrylate copolymers, polyacrylic acid esters, PVC and copolymers of ethylene and vinyl acetate which may be partially saponified.

Examples of such polymer latices may be found, for example, in US Patent No.

2,993,013 and German Offenlegungsschrift No. 2,014,385.

As examples of polycondensate dispersions may be mentioned the aminoplastic or phenoplast dispersions which may contain ionic groups as described in German Offenlegungsschrift No. 2,324,134. Methylolated polycondensate dispersions prepared using an excess of formaldehyde may also be used.

According to a special embodiment of the prese process of the polyisocyanate polyaddition reaction the polyurethane resins produced from the dispersions obtainable according to the invention can be optimally improved and modified in their properties exactly as desired by suitable choice of their starting compounds because of the very wide range of possible reactants available for selection.

Thus, for example, very interesting combinations of cationic and anionic solid particles can be obtained in the end product by the process according to the invention.

According to another variation of the process according to the invention, aqueous solutions of ionic, linear polyurethanes are used as starting materials instead of aqueous polymer dispersions. Such solutions are obtained if, in the preparation of a linear polyurethane, the diisocycanate is reacted almost exclusively with diols or diamines which contain ionic or ionogenic groups (see the publication by D. Dieterich et al. in Angewandte Chemie 82, 1970, pages 8363 mentioned above).

The various starting components used in the process according to the invention are selected according to the proposed use of the polyurethanes prepared from the modified polyhydroxyl compounds obtainable according to the invention and according to the desired modification or improvement in their mechanical properties or possible methods of application. If, for example, it is desired to modify a relatively hard, brittle polyurethane in order to increase its impact strength, an aqueous dispersion of a highly elastic polyurethane, polymer or polycondensate should be used.

It is thereby possible not only to reduce substantially the general brittleness of the end product but also to increase the elasticity of the surface zones which are particularly liable to be damaged by impact, for example in the case of a foam product.

It is, of course, also possible to proceed conyersely on the same principle and to modify a relatively soft polyurethane product by means of a dispersion of a relatively hard polyurethane, polymer or polycondensation product. It is possible in this way to optimise both the hardness and the tensile strength of the end product. In addition, the stability of the products to light can be improved, for example when using finely disperse particles of poly hydrazodicarbonamides.

According to another possible variation of the present invention, polyisocyanate polyaddition products dispersed in the polyhydroxyl compounds are subsequently cross-linked with formaldehyde in known manner in the presence of catalytic quantities of acids. It is surprisingly found that cross-linked dispersions of this kind are also finely disperse and stable in storage.

The special importance of the present invention lies in the fact that all the above mentioned improvements and modifications in the properties of polyurethane resins can be obtained using the usual raw materials and conventional, in most cases standardised formulations.

Various methods may be employed for mixing the dispersing agent with the reactants In the simplest case, the hydroxyl containing dispersing agent, the necessary quantity of water or aqueous polymer latex and the amino or primary hydroxyl compound are introduced into a stirrer vessel and heated with stirring, for example to 70 to 900 C, and the isocyanate component is added rapidly so that the reaction mixture boils vigorously under reflux. When producing dispersions with a high solids content, it is advantageous to introduce the polyisocyanate or polyisocyanate mixture into the lower third of the liquid in the reaction vessel. If suitable stirrer apparatus are employed, the reaction temperature may be raised to 105 to 1 150C by employing a slight excess pressure. When the isocyanate groups have undergone complete reaction, the water and any inert solvent present are distilled off at reduced pressure and the dispersion discharged through a sieve. In many cases, the (aqueous) solution of amino compounds and polyisocyanate may1 of course, be introduced simultaneously into the dilution of external continuous phase in water. In that case, however, any excess of isocyanate should be avoided. Part of the heat of reaction may be used up by, for example, mixing the polyisocyanates with part of the alcohol used as external continuous phase at room temperature immediately before it is added to the reaction mixture. If the process according to the invention is desired to be carried out continuously, for example in the case of a large scale commercial product on of more than 1000 tons per month the external continuous phase, reactants and optionally water may be continuously fed into continuous flow mixers. In view of the strongly exothermic nature of the reaction, which increases with increasing solids content, and hence the increasing vapour pressure, the time of stay in the reactor must be so short that the reaction temperature in the premixer as far as possible does not exceed 100"C. When preparing a 40% dispersion, for example, the time required for the flow through the mixer should not be substantially above 1 to 3 seconds. The premixed reactants are then introduced into a final stirrer vessel in which they stay for 20 to 30 minutes before being forced into another vessel for removal of the water by distillation. It is advisable to use less water when carrying out the continuous flow mixing process than that used for the discontinuous process under reflux in a reaction vessel.

Distillation of water may also be carried out at a later stage, but the dispersions then obtained have a higher viscosity.

In practice, for obtaining very low viscosities, preference will be given to the discontinuous process in reaction vessels followed by immediate removal of water by distillation because of its great simplicity, reliability in reaction control and reproducibility.

The quantity of water required for subsequent reactions such as preparation of polyurethane foams may, of course, be left in the finished dispersion.

The concentration of polyaddition products in the dispersing agent containing hydroxyl groups may vary within a wide range but is generally between I and 75 /O by weight, particularly between 5 and 65% by weight. The dispersions prepared according to the invention have viscosities of up to 80,000 cP, preferably up to 40,000 cP, at 25"C., depending on their concentration.

After dilution to a solids content of 10% by weight, they generally have a viscosity below 2500, preferably below 1500 cP at 25"C. It is surprisingly found that if dispersions are prepared at very high concentrations and diluted to the desired final concentration, the products obtained have a lower viscosity than those directly prepared with the desired solids content.

As already explained above, dispersions having a surprisingly high solids content, up to 60% or more, can be prepared economically in stirrer vessels with reflux condensers in spite of the strongly exothermic reaction of isocyanate groups with amino groups. Since dispersions having a solids content of about 10% by weight are generally used for producing polyurethane resins, it is possible to mix the concentrated dispersions with high proportions by weight of those hydroxyl containing alcohols, e.g.

polyesters, which might partially react with water or amino compounds, e.g. hydrolysis or aminolysis, at the temperatures at which preparation of the dispersion is carried out.

Thus, for example, a 10% (20%) dispersion in which the proportion by weight of polyether to polyester is 1:8 (1:3) and which has a viscosity only slightly higher than that of the pure polyester can be obtained from a 50% polyhydrazodicarbonamide dispersion in polyether by stirring four times (1.5 times) its quantity of polyester into it (see Examples).

Compared with the possible analogous method of preparation of non-ionic dispersions, the process according to the invention, preferably carried out using chain lengthening agents containing salt groups, is surprisingly found to be generally simpler in practice to carry out because the water content in the reaction mixture is not very important. Satisfactory products are obtained both with relatively large and with relatively small quantities of water whereas, when preparing dispersions of nonionogenic products, it is generally necessary to keep the quantity of water within a more restricted range. The ions present evidently increase the compatibility between polyol and water by virtue of their hydrophilic character, but they also increase the compatibility between these components and the dispersed ionic solid matter.

The use of higher molecular weight hydroxyl polyethers as external continuous phases in the process according to the invention opens up the possibility, as already mentioned above, of a highly economic and variable method of commercial production carried out under mild conditions to produce dispersions having a high solids concentration which may, if desired, be used as master batches.

The use of polyethers has, however, yet another important advantage: The large scale commercial production of polyethers in most cases leads to the formation of intermediate stages of aqueous crude polyethers having a water content of from 8 to 12% and containing from 0.3 to 1% by weight of alkali metal sulphates in solution and, in addition, from 1 to 3% by weight of toluene in suspension. Such a crude polyether suspension is normally distilled under reduced pressure to reduce the water and toluene to a residue of from 0.4 to 1% by weight. The alkali metal sulphates are thereby precipitated and can be removed by means of sponge filters.

The polyether, now free from sulphonates and containing from 0.5 to 1% by weight of water, is substantially free from its residual water content by thin layer evaporation so that the purified commercial polyether contains less than 0.5% by weight of water.

For the process according to the invention, however, it is not necessary to use a highly purified, practically anhydrous polyether.

The preliminary crude polyether stages are satisfactory for the process, either the substance obtained before thin layer evaporation or, what is particularly advantageous, the so-called crude polyether suspensiontcontaining about 10% of water, alkali metal sulphate and toluene). In the process according to the invention, the water, toluene and sulphate are removed by distillation and filtration after termination of the isocyanate polyaddition reaction.

The dispersions prepared by the process according to the invention can be used as "modified" lower or higher molecular weight polyhydroxyl compounds in known manner in reactions with polyisocyanates of the kind mentioned above, to which unmodified polyhydroxyl compounds or polyamines, hydrazines or hydrazides of the kind mentioned above may be added as chain lengthening agents and blowing agents, catalysts and other additives may also be added to produce polyurethane resins with improved mechanical properties.

Examples of the products which may be produced include foams, elastomers, homogeneous and porous coatings, lacquers and thermoplastic polyurethanes. In addition, the products of the process may be used as such or after conversion to "modified" prepolymers by reaction with a polyisocyanate excess for producing aqueous polyurethane dispersions by known methods.

One factor which is of major importance in determining the improvement in properties produced by the products according to the invention in the resulting polyurethane resins, particularly the improvement in compression resistance and tensile strength, is the particle size of the dispersed polyaddition products. Thus, for example, when using polyether dispersions as starting materials for the production of polyurethane foams, the diameter of the particles of filler must be substantially below the dimensions of the cell walls (20 to 50 ,um). In polyurethane coatings, the particles must be small enough to ensure that even very thin coatings can be applied evenly and have a smooth surface.

The process according to the invention advantageously gives rise to dispersions having particles sizes of from 0.01 to 5 , tm, preferably 0.1 to 1 ,um, which satisfy the commercial requirements.

One particularly preferred purpose for which the ionic dispersions according to the invention are used is the production of foams which contain ionic groups, in other words foams which have been rendered hydrophilic. One of the characteristics of such hydrophilic foams, for example, is that they are wetted more easily and are capable, depending on their hydrophilic character, of absorbing larger quantities of water than conventional products. The foams may also be used, for example, as ionic exchangers.

The process for producing such foams which have been rendered hydrophilic is also a subject of this invention.

To produce such foams, the hydroxyl groups of the dispersing agent, which may also contain reactive groups still present in the dispersed polyurethane particles, are reacted with the isocyanates described above in the presence of blowing agents, for example in the presence of the water still left in the dispersions from the process used for preparing them.

According to one special variation of this process, aqueous polymer latices may be added to the reaction mixture before foaming for example by analogy to the process described in German Offenlegungsschrift No. 2,014,385 and US Patent No. 2,993,013. This modification can be used for further modifying the properties of the hydrophilic foams obtainable according to the invention.

The foams with ionic groups produced according to the invention have a substantially higher conductivity than conventional non-ionic products. They are very suitable for the known methods of high frequency welding techniques. The products also have a distinctly increased capacity for dye absorption.

If desired, other compounds which are reactive with isocyanates as well as catalysts, organic blowing agents, fillers and additives, may also be used.

Suitable organic blowing agents include e.g. acetone, ethyl acetate, halogenated alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane and dichlorodifluoromethane, also butane, hexane, heptane and diethylether. The action of a blowing agent can also be obtained by the addition of compounds which decompose at temperatures above room temperature to liberate gases such as nitrogen, e.g. azo compounds such as azoisobutyric acid nitrile. Other examples of blowing agents and details concerning the use of blowing agents may be found in Kunststoff Handbuch, Volume VII, published by Vieweg and Hchtlen, Carl Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453455 and 507-510.

Catalysts may in many cases be used according to the invention, including known catalysts such as tertiary amines, e.g.

triethylamine, tributylamine, N methylmorpholine, N - ethylmorpholine, N - cocomorpholine, N,N,N',N' tetramethylethylene diamine, 1,4 - diaza bicyclo - (2,2,2)- octane, N - methyl - N'- dimethyl - aminoethylpiperazine, N,N - dimethylbenzylamine, bis - (N,N diethylaminoethyl) adipate, N,N diethylbenzylamine, pentamethyldiethylenetriamine, N,N - dimethylcyclohexylamine, N,N,N',N' tetramethyl- 1,3 - butanediamine, N,N dimethyl - p- phenylethylamine, 1,2, - dimethylimidazole, and 2 methylimidazole. The known Mannich bases obtained from secondary amines such as dimethylamine and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone, cyclohexanone and phenols such as phenol itself, nonylphenol or bisphenol may also be used as catalysts.

Suitable catalysts in the form of tertiary amines having hydrogen atoms which are reactive with isocyanate groups include e.g.

triethanolamine, triisopropanolamine, Nmethyldiethanolamine, N - ethyl diethanolamine, N,N - di - methyl ethanolamine and their reaction products with alkylene oxides such as propylene oxide and/or ethylene oxide.

Silaamines having carbon-silicon bonds may also be used as catalysts, for example those described in German Patent Specification No. 1,229,290 and US Patent Specification No. 3,620,984, e.g. 2,2,4 - trimethyl- 2- silamorpholine and 1,3 diethylaminomethyl - tetramethyl disiloxane.

Basic nitrogen compounds such as tetralkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali metal phenolates such as sodium phenolate and alkali metal alcoholates such as sodium methylate may also be used as catalysts.

Hexahydrotriazines are also suitable catalysts.

Organic metal compounds may also be used as catalysts according to the invention, in particular organic tin compounds.

The organic tin compounds used are preferably tin (II) salts of carboxylic acids such as tin(II) acetate, tin(II) octoate, tin(II) ethyl hexoate and tin(II) laurate, and tin(IV) compounds such as dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate. Any of the above mentioned catalysts may, of course, be used as mixtures.

Other representatives of catalysts which may be used according to the invention and details concerning the action of the catalysts may be found in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 96 to 102.

The catalysts are generally used in a quantity of from about 0.001 to 10% by weight.

Surface-active additives such as emulsifiers and foam stabilizers may also be used when producing polyurethane foams according to the invention. Suitable emulsifiers include e.g. the sodium salts of ricinoleic sulphonates or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine. Alkali metal or ammonium salts of sulphonic acids such as dodecylbenzenesulphonic acid or dinaphthylmethane disulphonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids may also be used as surface active additives. Suitable foam stabilizers are, particularly, the polyether siloxanes, especially those which are water soluble. 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 for example, in US Patent Specifications No. 2,834,748; 2,917,480 and 3,629,308.

Other additives which may be used according to the invention include reaction retarders, e.g. substances which are acid in reaction such as hydrochloric acid or organic acid halides, cell regulators known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes, pigments, dyes and flame retarding agents known per se such as tris - chloroethylphosphate, tricresyl phosphate and ammonium phosphate and polyphosphate, stabilizers against ageing and weathering, plasticizers, fungistatic and bacteriostatic substances and fillers such as barium sulphate, kieselguhr, carbon black or whiting.

Other examples of surface active additives, foam stabilizers, cell regulators, reaction retarders, stabilizers, flame retarding substances, plasticizers, dyes, fillers and fungistatic and bacteriostatic substances which may also be used according to the invention and details concerning their use and mode of action may be found in Kunststoff Handbuch, Volume VII, published by Vieweg and Hchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113.

The components used for production of the foams are reacted according to the invention by the known one-shot, prepolymer or semiprepolymer process, in many cases using mechanical devices such as those described in US Patent Specification No. 2,764,565. Details concerning processing apparatus which may be used according to the invention may be found in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hchtlen, Carl Hanser-Verlag, Munich 1966, e.g. on pages 121 to 205.

The foaming reaction for producing the foams is often carried out inside moulds.

The reaction mixture is introduced into a mould made of a metal such as aluminium or a synthetic product such as epoxide resin and is foamed up inside the mould to produce the shaped product. Foaming inside moulds may be carried out either to produce articles having a cellular structure on their surface or to produce articles having a compact skin and cellular centre.

According to the invention, one or other effect can be achieved by either introducing just sufficient reaction mixture into the mould to fill the mould after foaming or introducing a larger quantity of reaction mixture. The latter method is known as "overcharging", a procedure which has been described, for example, in US Patent Specifications No. 1,178,490 and No.

3,182,104.

The process of foaming in moulds is frequently carried out using known "external mould release agents" such as silicone oils but so-called "internal mould release agents" may also be used, optionally in admixture with external mould release agents, e.g. as disclosed in German Offenlegungsschriften No. 2,121,670 and 2,307,589.

Cold setting foams can also be produced according to the invention as described in British Patent Specification No. 1,162,517 and German Offenlegungsschrift No.

2,153,086.

Foams may, of course, also be produced by the process of block foaming or by the known laminator process.

The following Examples serve to explain the process according to the invention. The figures given represent parts by weight or percentages by weight unless otherwise indicated.

Example 1 20% Anionic polyurea dispersion in trifunctional polyether.

NCO Index ( .100)=100 NH Anion equivalent quantity=0.275/100 g of solid matter Reaction mixture: 80.0 parts by weight of a polyether of propylene oxide and ethylene oxide started on trimethylol propane and having a hydroxyl number of 34 and containing about 80% of primary hydroxyl groups (hereinafter referred to "polyether I") as external continuous phase; 9.6 parts by weight of tolylene diisocyanate (isomeric mixture 2,4:2,6=80:20) hereinafter referred to as "T 80"; 10.4 parts by weight of aliphatic diamine sulphonate H2N-CH2-CH2-NH-CH2-CH2-SO3Na, hereinafter referred to as "AAS-salt" (used as 45% aqueous solution); and a total of 11% by weight of water, based on the quantity of reaction mixture including water (=15.3%, based on external continuous phase; 61.3% based on solid matter; 12.3% based on anhydrous dispersion).

Preparation of the dispersion A mixture of external continuous phase and aqueous solution is heated to 450C in a stirrer vessel equipped with reflux condenser. The isocyanate is then rapidly stirred in so that the heat released by the exothermic reaction raised the temperature to 80 to 1000C. Stirring is continued for 20 to 30 minutes after all the isocyanate has been added. Water is finally distilled off at reduced pressure. The resulting very finely divided, stable, 20% dispersion containing a residue of 0.6% of water has a viscosity of 2400 cP/25 C.

Example 2 12% Anionic polyurea dispersion in trifunctional polyether.

Index=128 Anion equivalent quantity=0.242/100 g of solid matter.

Reaction mixture: 88.0 parts by weight of polyether I; 6.5 parts by weight of diisocyanate T 80; 5.5 parts by weight of AAS salt; 6.1 by weight of water, based on reaction mixture including water (7.4% based on external continuous phase; 54.2% based on solid matter; 6.5 /" based on anhydrous dispersion).

The method is similar to that described in Example 1. The resulting, finely divided dispersion which has a solid content of 12% and contains a residue of 0.2% of water has a viscosity of 2400 cP/250C.

Example 3 22.3% Anionic polyurea dispersion in trifunctional polyether.

Index=100 Anion equivalent quantity=0.27/100 g of solid matter.

Reaction mixture: 77.7 parts by weight of polyether I; 7.7 parts by weight of diisocyanate T 80; 3.3 parts by weight of phenyl isocyanate; 11.3 parts by weight of AAS salt; 11.6%, by weight of water, based on reaction mixture including water (=17% based on external continuous phase; 59.3% based on solid matter; 13.2% based on anhydrous end product).

The procedure is similar to that of Example 1. A 22.3% dispersion containing a residue of 0.4% of water and having a viscosity of 2850 cP/25 C is obtained.

Example 4 14.2% Polyurea - polyhydrazodicarbonamide dispersion in trifunctional polyether.

* Index=100 Anion equivalent quantity=0.043/100 g solid matter.

Reaction mixture: 85.8 parts by weight of polyether I; 11.2 parts by weight of diisocyanate T 80, 1.1 part by weight of AAS salt 1.9 parts by weight of hydrazine (in the form of 99 ,' hydrazine hydrate; added together with the AAS salt solution), and a total of 2.3 /, by weight of water, based on the reaction mixture including water (=2.8% based on external continuous phase, 16.8% based on solid matter, 2.4% based on anhydrous dispersion).

Preparation of the dispersion The 45% aqueous AAS salt solution and hydrazine hydrate are mixed with the external continuous phase in a stirrer vessel and the reaction is then started by the addition of diisocyanate at room temperature. The reaction temperature rises to 6e80"C. After 60 minutes, water is distilled off at reduced pressure.

The resulting stable 14.2% dispersion which still contains a residue of 0.3 /" of water has a viscosity of 6300 cP/25 C. After dilution to 10% with a further quantity of.

polyether I, it has a viscosity of 3400 cP/25 C.

Comparison experiment: When no aqueous AAS salt solution is used, i.e. when hydrazine hydrate is used alone under otherwise the same reaction conditions and at the same index, a nonionic 14% paste having a viscosity of 125,000 cP/25 C is obtained.

Example 5 39.1 Polyurea polyhydrazo dicarbonamide dispersion in trifunctional polyether.

Index=100 Anion equivalent content=0.03/100 g of solid matter.

Reaction mixture: 60.9 parts by weight of polyether I, 31.5 parts by weight of diisocyanate T 80, 2.1 parts by weight of AAS salt, 5.5 parts by weight of hydrazine (as 99% hydrate), 23.8% by weight of water based on reaction mixture including water (51.5% based on external continuous phase, 80% based on solid matter, 31.3% based on anhydrous dispersion).

Preparation of the dispersion The reaction vessel used is a stirrer vessel with highly efficient reflux condenser and an inlet tube with non-return valve in the lower third of the reaction vessel. The external continuous phase, heated to 800 C, is mixed with the diluted aqueous solution of hydrazine hydrate and AAS salt. The diisocyanate is then forced in so rapidly at the same temperature, with stirring that polyaddition proceeds under vigorous reflux. Distillation of water is started after 10 minutes at reduced pressure. The temperature rises to 1100C towards the end of the reaction, and the practically anhydrous dispersion obtained is run through a 100 pm sieve. The very finely divided and stable 39.1% dispersion obtained in this way has a viscosity of 11,500 cP/25 C. When diluted to 20% by weight or 10% by weight with polyether I, the dispersion has a viscosity of 2100 cP or 1310 cP/25 C. If, on the other hand, the water is distilled off only after 2 days, difficulties arise when attempts are made to heat the highly viscous paste, which contains 23.8% of water, when it has cooled to room temperature. Furthermore, the viscosity of the anhydrous dispersion is between 2.5 and 4 times higher, dependi the form of a crude ether suspension containing 120/:, by weight of water and 0.7so by weight of alkali metal sulphate; 31.0 parts by weight of diisocyanate T 80, 2.2 parts by weight of AAS salt, 1.8 parts by weight of diethanolamine, 5.0 parts by weight of hydrazine hydrate (in the form of the 99 Mn hydrate diluted with water) and a total of 20% by weight of water, based on the reaction mixture including water (41.6 Mn based on external continuous phase, 62.5% based on solid matter, 25% based on anhydrous dispersion).

The procedure employed for preparing the dispersion is similar to that of Example 5. The resulting, very finely divided dispersion has a viscosity of 5290 (or 1750 or 1050) cP/25 C at a concentration of 40% (or 20% or 10%).

Example 7a When the 40% dispersion in polyether obtained according to Example 7 is diluted with the same polyester as in Example 6, stable polyurea dispersions are obtained (polyether: polyester=3:5 or 1:5) which at concentrations of 20% and 10% have a viscosity of 17,200 cP/25 C or 21,000 cP/25 C.

Example 7b When Example 7 is repeated but the quantity of polyester in the reaction mixture is reduced so that the concentration of solid matter is 50% and, if a total of 20% by weight of water is used, based on the quantity of reaction mixture (50% based on external continuous phase or solid matter, 25% based on anhydrous dispersion), a very finely divided, stable dispersion having a viscosity of 6150 cP/25 C is obtained. When this is diluted with pure dispersing agent to a solid content of 40%, 20% or 10%, the resulting dispersions have viscosities of 3400, 1480 and 1030 cP/25 C.

Example 7c If Example 7 is repeated but the quantity of polyether is modified so that the solid content of the resulting dispersion is 60% and if a total of 20% by weight of water is added, based on the quantity of reaction mixture (62.5% based on external continuous phase, 41.6% based on solid matter, 25% based on anhydrous dispersion), a finely divided, stable dispersion having a viscosity of 28,700 cP/25 C is obtained. When the dispersion is diluted to a solid content of 40%, 20% or 10%, the resulting viscosities are 3800, 1550 and 1080 cP/25 C.

Example 8 17.8% polyurea - polyhydrazo dicarbonamide dispersion in trifunctional polyether.

Index 100 Carboxylate - ion equivalent quantity=0.04/100 g of solid matter.

Reaction mixture: 82.2 parts by weight of a polyethylene oxide, started on trimethylolpropane, (OH number 550, hereinafter referred to as polyether II); 15.2 parts by weight of tolylene diisocyanate (mixture of isomers 2,4:2,6=65:35); 1.4 parts by weight of hydrazine (in the form of 99% hydrate diluted with water); 1.2 parts by weight of the diaminocarboxylate of the formula H2N-CH2-CH2-NH- C112-CH2-COOLi and a total of 10% by weight of water, based on the quantity of reaction mixture including water (13.8% based on external continuous phase, 59.5% based on solid matter, 11.2% based on anhydrous dispersion).

A finely divided 17.8% dispersion having a viscosity of 3200 cP/25 C is obtained under the reaction conditions indicated in Example 5. When the dispersion is diluted to 10% using pure external continuous phase, the resulting viscosity is 2100 cP/250C.

Example 9 14.2% Polyurea - polyhydrazodicarbonamide dispersion in linear polyether.

Index=100 Sulphonate - ion equivalent content=0.04/100 g of solid matter.

Reaction mixture: 85.8 parts by weight of a linear polypropylene glycol having secondary hydroxyl groups (hydroxyl number 56, hereinafter referred to as polyether III); 10.5 parts by weight of diisocyanate T 80, 1.8- parts by weight of hydrazine (used as 99% hydrate), 1.9 parts by weight of diaminosulphonate of the formula

10% by weight of water, based on the quantity of reaction mixture including water (13.8% based on external continuous phase 59.5% based on solid matter, 11.2 'n based on anhydrous dispersion).

When the general method of procedure described in Example 1 is employed, a stable 14.2% dispersion having a viscosity of 3,800 cP/25 C is obtained. When this is diluted to 10% with pure external continuous phase, the diluted dispersion has a viscosity of 2250 cP/25 C.

Comparison Example: When only 1% by weight of water instead of 10% is used in the reaction mixture under otherwise identical conditions, a paste having a viscosity of 280,000 cP/25 C is obtained.

Example 9a If a 14% polyether dispersion is prepared in a manner analogous to Example 9 using a mixture of 5.22 parts by weight of diisocyanate T 80 and 7.5 parts by weight of 4,4' - diphenylmethane diisocyanate, a stable dispersion having a viscosity of 4500 cP/25 C when anhydrous at a solid content of 14% and a viscosity of 2550 cP/250C at a solid content of 10% is obtained.

Example 10 20% Cationic polyurethane dispersion in linear polyether.

Index=100 Cation equivalent quantity=0.34/100 g of solid matter.

Reaction mixture: 80.0 Parts by weight of polyether III; 11.8 parts by weight of diisocyanate T 80, 8.2 parts by weight of N methyldiethanolamine, 7% by weight of water, based on the total quantity of reaction mixture.

Method of Preparation Polyether, water and N-methyl diethanolamine are mixed in a vessel equipped with stirrer. The diisocyanate is then added slowly with cooling so that the reaction temperature does not rise above 50"C. The water is distilled off at reduced pressure 60 minutes after all the diisocyanate has been added. Towards the end of distillation, the temperature is gradually raised to 900 C. A dispersion having a viscosity of 2110 cP/25 C is obtained. This dispersion is quaternised in a second stage: An equivalent quantity (based on tertiary nitrogen) of dimethylsulphate diluted with 4 times its quantity by weight of pure external continuous phase is gradually introduced into the dispersion with vigorous stirring.

The reaction mixture is kept at 60 to 700C for 30 minutes with stirring to complete the reaction. The finely divided cationic dispersion obtained has a viscosity of 1380 cP/25 C at a solids content of 20%.

Example 11 9.5% Cationic polyurea - polyhydrazodicarbonamide dispersion in trifunctional polyether.

Index=100 Cation equivalent content=0.04/100 of solid matter.

Reaction mixture: 90.5 parts by weight of polyether I, 7.3 parts by weight of diisocyanate T 80, 1.2 parts by weight of hydrazine (added in the form of 99 /n hydrazine hydrate), 0.6 parts by weight of triamine of the formula

0.4 parts by weight of dimethylsulphate, 10% by weight of water, based on the quantity of reaction mixture (practically completely removed by distillation before quaternisation is carried out).

The method employed in the first stage (preparation of dispersion) is analogous to that of Example 1 and in the second stage (quaternisation) analogous to that of Example 10. A stable cationic 9.5% dispersion having a viscosity of 2350 cP/25 C is obtained.

Example 12 4% polyurea dispersion in copolyester.

Index=50 Ion equivalent content=0.364/100 g of solid matter.

Reaction mixture: 96 parts by weight of copolyester from 1,6 - hexanediol neopentyl glycol and adipic acid (OH number 63, acid number 1.5), 1.2 parts by weight of 1,6 hexamethylenediisocyanate, 2.8 parts by weight of AAS salt, 3.1 /n by weight of water, based on the quantity of reaction mixture (3.4% based on external continuous phase 81.3% based on solid matter, 3.2% based on end product).

The method is similar to that of Example 1. An anhydrous polyester dispersion is obtained which has a softening point 25"C lower than that of the pure polyester.

Example 13 33.7US Polyurea dispersion in tetraethylene glycol.

Reaction mixture: 66.3 parts by weight of tetraethyleneglycol, 16.6 parts by weight of diisocyanate T 80, 17.1 parts by weight of AAS (as aqueous solution) and a total of 20% by weight of water, based on the total quantity of reaction mixture (38% based on external continuous phase, 74.6% based on solid matter, 25% based on anhydrous dispersion).

The method is similar to that of Example 1. A stable, finely divided dispersion having a viscosity of 2950 cP/250C is obtained.

The following Examples illustrate the use of the ionic dispersions according to the invention for producing soft foams and cold setting, highly elastic polyurethane foams or elastomers and aqueous polyurethane dispersions.

Example 14 100 parts by weight of anionic polyhydrazodicarbonamidepolyether dispersion from Example 5 adjusted to a solid content of 10%, 2.7 parts by weight of water, 0.03 parts by weight of triethylamine, 0.2 parts by weight of 2 dimethylamino - ethanol, 0.8 parts by weight of commercial polysiloxane stabilizer (OS 20 of Bayer AG) and 0.35 parts by weight of tin-(II) octoate are mixed together. The mixture is vigorously stirred together with 33.4 parts by weight of tolylene diisocyanate (65% 2,4- and 35% 2,6 - isomer) at room temperature.

A creamy reaction mixture forms within 7 seconds. It has a rise time of 70 seconds and a gel time of 115 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 41 kg/m3 Tensile strength according to DIN 53571 160 kPa Elongation at break according to DIN 53571 195% Compression resistance according to DIN 53577 6.3 KPa Indentation hardness according to ASTM D 1564--71T: H-value at 25% deformation 302 H-value at 65% deformation 597 RH-value at 25% deformation 194 (25% RH-value/25% H-value)x100 66% 65% H-value/25% H-value 2.0 The specific electric resistance of this foam according to DIN 52 482 is 6.2x 10'2Ohm.cm whereas a comparable foam produced without a polyether having ionic groups has a corresponding resistance of 2.1x10'3 Ohm.cm.

Example 15 100 Parts by weight of the dispersion from Example 14, 5.5 parts by weight of water, 0.03 parts by weight of triethylenediamine, 0.3 parts by weight of 2 dimethylaminoethanol, 1.5 parts by weight of polysiloxane stabilizer (OS 20 of Bayer AG) and 0.35 parts by weight of tin-(II) octoate are mixed together. 59.8 Parts by weight of tolylene diisocyanate (65%, 2,4-isomer and 35% 2,6-isomer) are added to this mixture with vigorous stirring at room temperature.

A creamy reaction mixture is formed after 6 seconds. It has a rise time of 78 seconds and a gel time of 124 seconds.

The foam obtained is found to have the following mechanical properties: Gross density according to DIN 53420 22 kg/m3 Tensile strength according to DIN 53571 135 KPa Elongation at break according to DIN 53571 170% Compression resistance according to DIN 53577 3.8 KPa Indentation hardness according to ASTM D 156-71T H-value at 25% deformation 128 H-value at 65% deformation 260 RH-value at 25% deformation 82 (25% RH-value/25% H-value)x 100 64% 65 H-value/25% H-value 2.0 The following Examples demonstrate the manufacture of a cold setting, highly elastic polyurethane foam.

Example 16 100 Parts by weight of the dispersion used in Example 14, 3.0 parts by weight of water, 0.1 part by weight of triethylene diamine, 0.3 parts by weight of 2 dimethylamino - ethanol, 1.0 part by weight of a commercial polysiloxane polyether manufactured by Goldschmidt (B 3207) 2.0 parts by weight of diethanolamine and 2.0 parts by weight of trichlorethyl phosphate are mixed together. 38.1 parts by weight of tolylene diisocyanate (80% 2,4- isomer and 20% 2,6 isomer) are added to this mixture at room temperature and mixed. A creamy reaction mixture is formed after 7 seconds. It has a rise time of 135 seconds and a gel time of 148 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 36 kg/m3 Tensile strength according to DIN 53571 95 KPa Elongation at break according to DIN 53571 150% Compression resistance according to DIN 53577 2.4 KPa Indentation hardness according to ASTM D 1564--71T: H-value at 25% deformation 93 H-value at 65% deformation 218 RH value at 25% deformation 76 (25% RH-value/25% H-value)x 100 82% 65% H-value/25% H-value 2.4 Example 17 100 Parts by weight of the dispersion according to Example 14, 3.0 parts by weight of water, 0.06 parts by weight of triethylene diamine, 0.2 parts by weight of 2 dimethylaminoethanol, 1.0 part by weight of a commercial siloxane stabilizer manufactured by Goldschmidt (B 3207), 2.0 parts by weight of diethanolamine and 2.0 parts by weight of trichloroethylphosphate are mixed together. 38.1 Parts by weight of tolylene diisocyanate (80% 2,4 - isomer and 20% 2,6 - isomer) are added to the mixture at room temperature and the components are vigorously mixed while air is added at an excess pressure of 0.5 atmospheres. A creamy reaction mixture forms after 8 seconds. It has a rise time of 145 seconds and a gel time of 163 seconds.

The foam obtained is found to have the following mechanical properties: Gross density according to DIN 53420 41 kg/m3 Tensile strength according to DIN 53571 130 KPa Elongation at break according to DIN 53571 95 , Compression resistance according to DIN 53577 3.6 KPa Indentation hardness according to ASTM D 1564--71T: H-value at 25% deformation 82 H-value at 65% deformation 208 RH-value at 25% deformation 68 (25% RH-value/25% H-value)x 100 85% 65% H-value/25% H-value 2.5 Example 18 100 Parts by weight of the cationic dispersion of Example 11 adjusted to a solid content of 9.5%, 2.7 parts by weight of water, 0.1 part by weight of triethylenediamine, 0.3 parts by weight of 2 dimethylaminoethanol, 0.8 parts by weight of polysiloxane stabilizer (OS 15 of Bayer AG) and 0.2 parts by weight of tin-(II) octoate are stirred together. 33.4 Parts by weight of tolylene diisocyanate (80% 2,4-isomer and 20% 2,6-isomer) are added to this mixture at room temperature and the mixture is vigorously stirred. A creamy reaction mixture which has a rise time of 240 seconds is formed after 15 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 40 kg/m3 Tensile strength according to DIN 53571 150 KPa Elongation at break according to DIN 53571 160% Compression resistance according to DIN 53577 6.1 KPa Pressure deformation residue: (2'h at 70"C 900,,) according to DIN 53572 9.9 Example 19 100 Parts by weight of the cationic dispersion used in Example 18, 3.0 parts by weight of water, 0.1 part by weight of triethylenediamine, 0.3 parts by weight of 2 dimethyiaminoethano 1.0 parts bv weight of a commercial polysiloxane polyether of Goldschmidt (B 3207), '.0 parts by weight of diethanolamine and 2.0 parts by weight of trichloroethylphosphate are mixed together. 37.4 parts by weight of tolylene diisocyanate (80% 2,4 - isomer and 20% 2,6-isomer) are vigorously stirred into the mixture at room temperature. A creamy reaction mixture which has a rise time of 118 seconds is obtained after 10 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 31 kg/m3 Tensile strength according to DIN 53571 90 KPa Elongation at break according to DIN 53571 100% Compression resistance according to DIN 53577 3.7 KPa Pressure deformation residue (22 h at 70"C 90%) according to DIN 53572 6.4 Example 20 Preparation of a 40% aqueous polyurethane dispersion.

The anionic 4% polyurea dispersion in a polyester obtained according to Example 12 is converted into a polyisocyanate prepolymer by reaction with excess 1,6 - hexamethylene diisocyanate (index=190) at 80 to 1200C.

The prepolymer is cooled to 50--600C and an aqueous 1,2 - propylene diamine solution (index=120) containing 10% by weight acetone (based on the prepolymer) is rapidly added. The small proportion of solvent present is subsequently distilled off.

The resulting stable aqueous 40% dispersion has a viscosity of 850 cP at 250C and can be used, for example, for coating textiles.

Comparison experiment: When preparation of the isocyanate prepolymer is carried out directly in the presence of the AAS salt, normally present in the form of a 45 /" aqueous solution, gelling occurs within 10 to 20 minutes.

When employing the conventional procedure, it is therefore necessary first to prepare a non-ionic prepolymer and then to dissolve this in about twice its quantity of acetone, based on the prepolymer (i.e.

about 20 times the quantity of solvent used in Example 20) before the water and diamine may be added. Finally, all the acetone must be distilled off.

Example 21 100 Parts by weight of the polyurea dispersion (dispersed in polyester: polyether=5:1) according to Example 7a. adjusted to a solid content of 10%, 4.0 parts by weight of water, 0.6 parts by weight of dimethylbenzylamine; 0.1 part by weight of tin-(II) octoate, 2.0 parts by weight of a commercial polysiloxane foam stabilizer (OS 25 of Bayer AG) are mixed together. The mixture is vigorously stirred together with 22.2 parts by weight of diisocyanate T 80 at room temperature.

A creamy reaction mixture forms after 10 seconds. It has a rise time of 65 seconds and a gel time of 125 seconds.

In contrast to the usual pure polyester foams, the foam obtained has open cells and, owing to its uniform, very fine cell structure it may be used e.g. as filter material. If the example is repeated using a mixture of unmodified pure polyester and polyether in the same proportions, an open cell foam is again obtained but it has substantially larger cells.

The mixture of pure polyester and polyether separates within a short time into two phases when left to stand at room temperature.

Example 22 Preparation of a homogeneous polyether - polyurethane elastomer.

The 50% polyether dispersion obtained according to Example 7b is reacted with excess 4,4' - diphenylmethane diisocyanate at 100 to 120"C to produce an isocyanate prepolymer containing 2.3% by weight of free isocyanate groups. 1,4 - butanediol (index=104) is stirred into the prepolymer at the same temperature. The highly viscous melt is poured out on to a surface (metal or glass) within 10 to 15 minutes and drawn out to a film of 250 pm using a doctor knife.

The film is then heated at 1300C, cooled and stripped from its substrate. The tensile strength of the film is 212 Kp/cm2, its elongation at break 180% and its Shore A hardness 77. The elastomer is insoluble even in hot dimethylformamide.

Comparison experiment: When the pure polyether is used instead of the dispersion but the reaction mixture is otherwise kept the same, a sticky polyether - polyurethane film is obtained which has so little tensile strength that it cannot be stripped from its substrate.

Example 23 A mixture of 25 parts by weight of the 40% anionic dispersion according to Example 7, 75 parts by weight of a copolyether of 10% ethylene oxide and 90% propylene oxide started on trimethylolpropane (hydroxyl number 42), 8.4 parts by weight of a 64.6 aqueous polyvinyl chloride dispersion, 0.8 parts by weight of 2 dimethylaminoethanol, 0.3 parts by weight of polysiloxane foam stabilizer (OS 20 of Bayer AG) and 0.1 part by weight of tin-(II) octoate is vigorously stirred together with 38.2 parts by weight of diisocyanate T 80.

A creamy reaction mixture forms after 14 seconds. It has a rise time of 131 seconds.

The foam obtained is found to have the following mechanical properties: Gross density according to DIN 53420 24 kg/m3 Tensile strength according to DIN 53571 145 KPa Elongation at break according to DIN 53571 120% Compression resistance according to DIN 53547 4.2 KPa Example 24 A mixture of 100 parts by weight of the same polyether mixture as in Example 23, 7.5 parts by weight of a 33% aqueous ABS polymer dispersion 0.1 part by weight of triethylene diamine, 0.3 part by weight of 2 dimethylaminoethanol, 0.6 parts by weight of polysiloxane foam stabilizer (OS 20 of Bayer AG) and 0.2 parts by weight of tin-(II) octoate is vigorously stirred together with 59.2 parts by weight of diisocyanate T 80.

A creamy reaction mixture forms after 15 seconds. It has a rise time of 85 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 21 kg/m3 Tensile strength according to DIN 53571 90 KPa Elongation at break according to DIN 53571 100% Compression resistance according to DIN 53577 4.1 KPa Example 25 A mixture of 100 parts by weight of the polyether mixture used in Example 23, 5.0 parts by weight of 40% aqueous copolymer dispersion of styrene and acrylonitrile, 0.8 parts by weight of 2 dimethylaminoethanol, 0.3 parts by weight of a polysiloxane foam stabilizer (OS 20 of Bayer AG) and 0.1 parts by weight of tin-(II) octoate is vigorously stirred together with 38.2 parts by weight of diisocyanate T 80.

A creamy reaction mixture which has a rise time of 145 seconds is formed after 14 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 34 kg/m3 Tensile strength according to DIN 53571 140 KPa Elongation at break according to DIN 53571 165% Compression resistance according to DIN 53577 4.6 KPa Example 26 Continuous method of carrying out the process of Example 1 in a multiphase reaction flow tube.

The reactants are stored in two storage vessels B 1 and B 2. Vessel B 1 contains a mixture of 8000 parts by weight of polyether I, 104 parts by weight of AAS salt and 127 parts by weight of water. Vessel B 2 contains 96 parts by weight of diisocyanate T 80. The rate of feed is 103.1 g per minute from B 1 and 9.6 g per minute from B 2, making a total of 112.7 g per minute.

Method The mixture which has been heated to 95"C in B 1 and the diisocyanate which is kept at 20"C in B 2 are combined coaxially in a static mixer manufactured by Kenics (diameter 1/4 inch; 21 elements; volume approximately 3 ml) (residence time longer than 1.1 seconds) with the aid of a twin piston pump, and the mixture is delivered at a pressure of 2 to 3 bar into a steel reaction tube having a length of about 6 m and a diameter of about 9 mm in which the temperature of the reaction mixture is kept at 110 +5 C by external heating or cooling.

The reaction tube opens into a decompression vessel in which the practically anhydrous dispersion is stirred at 800C and a pressure of 20 Torr during an average residence time of about 6 to 10 minutes. The decompression vessel is connected to a distillation bridge and via a pump to a further vessel which receives the end product. The resulting finely divided dispersion has a viscosity of 2050 cP at 25"C.

Example 27 Example 7 is repeated, but using the internal salt of diaminodisulphonic acid of the following formula

("dibetaine") instead of the AAS salt indicated in the formulation. This dibetaine, however, must be dissolved in diethanolamine and hydrazine monohydrate (30 /n at 1000C in water). A very finely divided dispersion which has free sulphonic acid groups is obtained.

At a concentration of 40%, it has a viscosity of 4450 cP at 250C.

Example 28 20% Anionic polyurea dispersion in Polyether I. Anion equivalent quantity =0.13/100 g of solids content.

Formulation 1562 parts by weight of Polyether I; 20.76 parts by weight 46% aqueous AAS salt solution; 136 parts by weight of 25% aqueous ammonia solution; 261 parts by weight of 2,4 - tolylene diisocyanate (hereinafter referred to as T 100).

Water content 11% by weight based on anhydrous dispersion.

Reaction conditions The dispersing agent and aqueous solutions of the amino functional compounds are introduced into the reaction vessel as described in Example 1 and the diisocyanate is introduced into the liquid phase of the reaction mixture at such a rate that the temperature is raised from 400C to 80"C by the exothermic reaction.

The anhydrous 20% (10%) dispersion has a viscosity of 4900 (735) cP at 250C.

Example 29 20% Anionic polyurea dispersion in polyether III. Anion equivalent quantity: 0.17/100 g of solid content.

Formulation 1164 Parts by weight of polyether III; 204 parts by weight of 46.5% aqueous AAS salt solution; 34 parts by weight of 25% aqueous ammonia solution; 187.5 parts by weight of 4,4' diphenylmethane diisocyanate (hereinafter referred to as diisocyanate D 44) The total water content is 8.6 /n by weight, based on the anhydrous dispersion.

The method is the same as in Example 28 but in this case diisocyanate D 44 heated to 80"C is introduced into the reaction mixture kept at 25 to 300 C, and the temperature is adjusted by cooling so that it does not exceed 65"C.

The 20% (10%) anhydrous dispersion has a viscosity of 1820 (1150) cP at 25"C.

Example 30 An aqueous formalin solution (5% by weight formaldehyde, based on the solid content of the dispersion) and a catalytic quantity of toluene sulphonic acid are added to the dispersion obtained in Example 29, optionally before the water is removed from the dispersion by distillation, and the temperature of the mixture is gradually raised from 40 to 950C over a period of 60 to 90 minutes with stirring. The water is then distilled off at reduced pressure.

The resulting anionic polyurea dispersion which contains polymethylene urea groups has a viscosity of 1890 cP at a concentration of 20%.

A polyurethane foam produced from this dispersion has a higher compression resistance than a foam produced from the unmodified dispersion of Example 29.

Example 31 20% Anionic polyurea dispersion in polyether III. Anion equivalent quantity: 0.18/100 g of solid content.

Formulation 1164 Parts by weight of polyether III; 204 parts by weight of 46.5% aqueous AAS salt solution; 34 parts by weight of 25% aqueous ammonia solution; 43.5 parts by weight of diisocyanate T 100; 125 parts by weight of diisocyanate D 44 The total water content is 8.4% by weight, based on the anhydrous dispersion.

The method is analogous to that of Example 28 but diisocyanate T 100 is first added at 20 to 300 C, and thereafter diisocyanate D 44 (heated to 800 C) is added at 30 to 55"C.

The resulting finely divided, anhydrous, 20% dispersion has a viscosity of 1190 cP at 25 C.

Example 32 40 /n APHS/SAN (anionic polyurea/ styrene - acrylonitrile copolymer) dispersion in ethylene glycol; ratio by weight of solids contents=l:l.

Formulation: 547 Parts by weight of ethylene glycol as external continuous phase 455 parts by weight of a 40% aqueous styrene - acrylonitrile dispersion (ratio by weight of styrene: acrylonitrile=72:78), hereinafter referred to as "SAN-Latex", 207 Parts by weight of a 46% aqueous solution of a diamino - sulphonate of the formula H2N-CH2-CH2-NH-CH2-CH2- SO3O NaO+ (herei

Reaction conditions The diisocyanate is introduced with vigorous stirring into the liquid phase of the mixture of external continuous phase ABS dispersion and NH compounds which has been heated to 800 C, and the water is subsequently removed at reduced pressure.

The viscosity of the 20% dispersion is 2350 cP at 25"C.

Example 35 20% APHS/SAN polyether graft copolymer dispersion in polyether I.

Ratio of solid contents=l:l.

Formulation 1639.8 Parts by weight of a graft copolymer which has a solid content of 11.1% by weight and has been obtained by polymerisation of 72 parts by weight of styrene and 28 parts by weight of acrylonitrile in polyether I at 1200C in accordance with US Patent Specification No. 3,383,351 or German Patent Specification No. 1,152,536 (viscosity 1230 cP/25 C); 207 parts by weight of 46% AAS salt solution 87 parts by weight of tolylene diisocyanate (ratio of 2,4- and 2,6 isomers=4:1).

Index=100 Water content: 5.6% by weight.

The reaction is carried out under the conditions indicated in Example 32 but at a reaction temperature of 88--98"C.

The 20% (10%), finely divided dispersion has a viscosity of 3150 (1780) cP at 250C.

Example 36 20% APHS/SAN dispersion in a linear polypropylene glycol.

Ratio of solid contents=l:l.

Formulation 932 Parts by weight of a linear polypropylene glycol with secondary hydroxyl groups (hydroxyl number 56) as external continuous phase (hereinafter referred to as polyether II), 291.2 parts by weight of the 40% aqueous SAN-Latex from Example 32, 82.8 parts by weight of 46% AAS salt solution, 13.6 parts by weight of a 25% solution of ammonia in water, 75 parts by weight of 4,4' diisocyanatodiphenylmethane.

Index=100 Water content 17.1% by weight.

Reaction conditions: Diisocyanate D44 heated to 90--1100C is introduced into the liquid phase of the reaction mixture as described in Example 35.

The 20% dispersion has a viscosity of 1730 cP at 25"C.

Example 37 28 /n APHD/PMHS (polymethyleneurea) dispersion in trifunctional polyether.

Ratio of solid contents=2.5: 1.

Formulation 1395.0 Parts by weight of a 10% finely divided polymethylene urea dispersion in polyether I prepared from equimolar quantities of urea and formalin in accordance with German Offenlegungsschrift No. 2,324,134.

300.0 Parts by weight of a 50% solution of an aromatic diaminodisulphonate of the formula

35.3 parts by weight of hydrazine monohydrate (99%), 174.0 parts by weight of tolylene - 2,4 diisocyanate.

Index=100; Water content: 8.7% by weight.

Reaction conditions The polymethyleneurea dispersion in polyether I and aqueous diaminosulphonate and hydrazine solution are introduced into the reaction vessel as described in Example 34 and the diisocyanate is added rapidly so that the reaction mixture boils under mild reflux.

Alternatively, a previously prepared polymethylene urea dispersion may be used directly for the polyisocyanate polyaddition reaction (that is to say without first distilling off the water).

The 28% (14%) dispersion has a viscosity of 39,800 (3550) cP at 25"C.

Example 38 20% APHD/PUR elastomer dispersion in polyether I. Ratio of solids contents=3:1.

Formulation 1355.0 Parts by weight of polyether I as dispersing agent, 201.6 parts by weight of a 42% aqueous, anionic PUR elastomer dispersion obtained from a polyester of hexandiol, neopentyl glycol and adipic acid (molecular weight=1800), hexamethylene - 1,6 - diisocyanate and a diaminosulphonate of the formula H2N-CH2-CH2-NH-CH2-CH2- SO3#Na (Shore A hardness=60), 50.5 parts by weight of hydrazine monohydrate (99%), 11.9 parts by weight of 46% AAS salt solution, 196.3 parts by weight of tolylene - 2,4 diisocyanate.

Index=100; Water content: 8.0% by weight.

The reaction conditions are the same as in Example 36.

The 20% dispersion has a viscosity of 2700 cP at 25"C and shows a pronounced Tyndall effect.

5.0 parts by weight of a 40% aqueous copolymer dispersion of styrene and acrylonitrile, 0.8 parts by weight of 2 dimethylaminoethano 0.3 parts by weight of a polysiloxane foam stabilizer (OS 20 of Bayer AG) and 0.1 parts by weight tin-(II) octoate is vigorously stirred together with 38.2 parts by weight of diisocyanate T 80.

A creamy reaction mixture -which has a rise time of 145 seconds is formed after 14 seconds.

The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 34 kg/m3 Tensile strength according to DIN 53571 140 KPa Elongation at break according to DIN 53571 165 /" Compression resistance according to DIN 53577 4.6 KPa Claim 1 of our co-pending application No. 46746/76 (Serial No. 1,571,185), claims a process for the preparation of stable, relatively low viscosity dispersions of polyisocyanate - polyaddition products in hydroxyl containing compounds as external continuous phase, characterised in that a previously prepared aqueous dispersion polyurethane, polyurea or polyhydrazodicarbodimide is mixed with a compound which has at least 1 hydroxyl group and the boiling point above 100"C and a water present in the dispersion is completely or partially removed to a water content of up to 10% by weight, after preparation of the dispersion by distillation. We make no claim to the subject matter of this claim.

Subject to the foregoing disclaimer.

WHAT WE CLAIM IS: 1. A dispersion having a solids content of from 1 to 70% by weight of a polyisocyanate polyaddition product containing ionic groups, in a compound containing at least two hydroxyl groups and having a molecular weight of from 62 to 16,000, which dispersion may contain up to 50% by weight of water.

2. A dispersion as claimed in claim 1 which has a solids content of from 5 to 60% by weight.

3. A dispersion as claimed in claim 1 or claim 2 in which the polyisocyanate polyaddition product is a polyurea or a polyhydrazodicarbonamide.

4. A dispersion as claimed in anyof claims 1 to 3 in which the hydroxyl containing compound has a molecular weight of from 62 to 12,000.

5. A dispersion as claimed in claim 4 in which the hydroxyl containing compound has a molecular weight of from 106 to 8,000.

6. A dispersion as claimed in any of claims 1 to 5 in which the hydroxyl containing compound contains from 2 to 8 hydroxyl groups.

7. A dispersion as claimed in claim 6 in which the hydroxyl containing compound contains from 2 to 6 hydroxyl groups.

8. A dispersion as claimed in claim 7 in which the hydroxyl containing compound contains from 2 to 4 hydroxyl groups.

9. A dispersion as claimed in claim 1 substantially as herein described with reference to any of the Examples.

10. A process for the "in situ" preparation of a stable dispersion as claimed in any of claims 1 to 9 by the reaction of 1. an organic polyisocyanate with 2. a compound having primary and/or secondary amino groups and/or primary hydroxyl groups in 3. a compound having at least two hydroxyl groups which hydroxyl groups are less reactive towards isocyanates than the isocyanate reaction groups of compound 2, compound 3 having secondary hydroxyl groups if compounds with primary hydroxyl groups are used as compound 2, in the presence of up to 30 /,, by weight, based on the whole reaction mixture of water

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. 201.6 parts by weight of a 42% aqueous, anionic PUR elastomer dispersion obtained from a polyester of hexandiol, neopentyl glycol and adipic acid (molecular weight=1800), hexamethylene - 1,6 - diisocyanate and a diaminosulphonate of the formula H2N-CH2-CH2-NH-CH2-CH2- SO3#Na (Shore A hardness=60), 50.5 parts by weight of hydrazine monohydrate (99%), 11.9 parts by weight of 46% AAS salt solution, 196.3 parts by weight of tolylene - 2,4 diisocyanate. Index=100; Water content: 8.0% by weight. The reaction conditions are the same as in Example 36. The 20% dispersion has a viscosity of 2700 cP at 25"C and shows a pronounced Tyndall effect. 5.0 parts by weight of a 40% aqueous copolymer dispersion of styrene and acrylonitrile, 0.8 parts by weight of 2 dimethylaminoethano 0.3 parts by weight of a polysiloxane foam stabilizer (OS 20 of Bayer AG) and 0.1 parts by weight tin-(II) octoate is vigorously stirred together with 38.2 parts by weight of diisocyanate T 80. A creamy reaction mixture -which has a rise time of 145 seconds is formed after 14 seconds. The resulting foam is found to have the following mechanical properties: Gross density according to DIN 53420 34 kg/m3 Tensile strength according to DIN 53571 140 KPa Elongation at break according to DIN 53571 165 /" Compression resistance according to DIN 53577 4.6 KPa Claim 1 of our co-pending application No. 46746/76 (Serial No. 1,571,185), claims a process for the preparation of stable, relatively low viscosity dispersions of polyisocyanate - polyaddition products in hydroxyl containing compounds as external continuous phase, characterised in that a previously prepared aqueous dispersion polyurethane, polyurea or polyhydrazodicarbodimide is mixed with a compound which has at least 1 hydroxyl group and the boiling point above 100"C and a water present in the dispersion is completely or partially removed to a water content of up to 10% by weight, after preparation of the dispersion by distillation. We make no claim to the subject matter of this claim. Subject to the foregoing disclaimer. WHAT WE CLAIM IS:

1. A dispersion having a solids content of from 1 to 70% by weight of a polyisocyanate polyaddition product containing ionic groups, in a compound containing at least two hydroxyl groups and having a molecular weight of from 62 to 16,000, which dispersion may contain up to 50% by weight of water.

10. A process for the "in situ" preparation of a stable dispersion as claimed in any of claims 1 to 9 by the reaction of

1. an organic polyisocyanate with

2. a compound having primary and/or secondary amino groups and/or primary hydroxyl groups in

3. a compound having at least two hydroxyl groups which hydroxyl groups are less reactive towards isocyanates than the isocyanate reaction groups of compound 2, compound 3 having secondary hydroxyl groups if compounds with primary hydroxyl groups are used as compound 2, in the presence of up to 30 /,, by weight, based on the whole reaction mixture of water

characterised in that at least one of the components 1 or 2 has groups which are ionic and/or groups which are converted into ionic groups after the reaction of components 1 and 2.

11. A process as claimed in claim 10 in which the reaction is carried out discontinuously in stirrer vessels in the presence of from 5 to 50% by weight of water, based on the total quantity of reaction mixture.

12. A process as claimed in claim 10 in which the polyaddition reaction is carried out continuously in a continuous flow mixer.

13. A process as claimed in any of claims 10 to 12 in which the compound used as component 2 is a polyamine and/or a hydrazine and/or a hydrazide.

14. A process as claimed in any of claims 10 to 13 in which the dispersing agent used is an unpurified crude polyether containing water, solvents and alkali metal salts, such as is obtained from the commercial production of polyethers.

15. A process as claimed in any of claims 10 to 14 in which the water in the presence of which the reaction is carried out, is removed after the reaction.

16. A process as claimed in any of claims 10 to 15 in which the polyisocyanate polyaddition reaction is carried out in the presence of an aqueous polymer latex or the aqueous solution of an ionic polyurethane.

17. A process as claimed in claim 16 in which an aqueous polymer dispersion having a solids content of between 5 and 55% by weight is used.

18. A process as claimed in any of claims 10 to 15 in which the dispersion of a vinyl polymer or of a polycondensation product in the dispersing agent containing hydroxyl groups is first prepared in situ and the polyisocyanate polyaddition reaction is thereafter carried out in the presence of water.

19. A process as claimed in any of claims 10 to 15 in which a polymer dispersed in a non-aqueous organic medium is added to the dispersing agent containing hydroxyl groups and thereafter the polyisocyanate polyaddition reaction is carried out after the addition of water.

20. A process as claimed in claim 10 substantially as herein described with reference to any of the Examples.

21. A dispersion as claimed in any of claims 1 to 9 when prepared by a process as claimed in any of claims 10 to 20.

22. A process for the production of a polyurethane resin by the reaction of a polyisocyanate with a polyhydroxyl compound and optionally other compounds which are reactive towards isocyanates and optionally blowing agents, catalysts and other additives, in which the polyhydroxyl compound used is a dispersion as claimed in any of claims 1 to 9 or claim 21.

23. A process for the production of a polyurethane foam by the reaction of a polyisocyanate with a polyhydroxyl compound and optionally other compounds which are reactive with isocyanates, in the presence of blowing agents and optionally catalysts and other additives, in which the polyhydroxyl compound used is a dispersion as claimed in any of claims 1 to 9 or claim 21.

24. A process as claimed in claim 23 in which, before foaming is carried out, an aqueous polymer latex whose water content acts as blowing agent in the foaming reaction is added to the reaction mixture.

25. A polyurethane foam or resin when produced by a process as claimed in any of claims 22 to 24.