3,756,992 United States Patent Office Patented Sept. 4, 1973 1. 2 urethanes in water without the use of solvents. Thus for 3,756,992 example an ionic polypropylene glycol polyurethane which POLYURETHANE POLYELECTROLYTES AND has been modified with isocyanate groups in the terminal PROCESS FOR PREPARING SAME Dieter Dieterich, Leverkusen, Germany, assignor to Bayer positions can be injected in the form of a hot liquid into Aktiengesellschaft, Leverkusen, Germany Water or distributed in water by means of mechanical No Drawing. Continuation of abandoned application Ser. stirrers which produce high shearing forces. Dispersions No. 809,987, Mar. 24, 1969. This application Mar. 13, of high molecular weight polyurethanes can also be ob 1972, Ser. No. 234,315 tained in this way by reacting the emulsion droplets with Claims priority, application Germany, Mar. 27, 1968, the water. P 17 70 068.4 0. This procedure is, however, technically complicated and Int, CI. C08g 22/04 difficult to reproduce. Furthermore, it is in practice limited U.S. C. 260-77.5 Q 16 Claims to polyether polyurethanes of low viscosity. It is also known that polyurethanes which are dispersed or dissolved in water may be cross-linked by means of ABSTRACT OF THE DISCLOSURE 15 formaldehyde (German Pat. No. 1,187,012). In such a Polyurethanes are prepared by dispersing solid or liquid case, formaldehyde, compounds which give off formalde polyurethane polyelectrolytes containing methylol groups hyde or compounds which react like formaldehyde, are by mixing with water, subjecting the electrolytes to a heat added to the polyurethane dispersion in the course of its treatment of 25 to 200° C. and removing the water. preparation and then react with the polyurethane in a 20 cross-linking reaction during the subsequent drying. The addition of aqueous solutions of formaldehyde during the This is a continuation of application Ser. No. 809,987, synthesis of the polyurethane mass in the presence of free filed Mar. 24, 1969, and now abandoned. NCO groups is, of course, out of the question, since the This invention relates to polyurethane plastics and a water would immediately react with the free NCO groups, method of production. More particularly, it relates to an 25 which would lead to the formation of a gelled mass. improved process for preparing new aqueous polyurethane It may, therefore, be said that polyurethane dispersions dispersions. having good technological properties could hitherto only Numerous processes are already known for the prepara be produced, in practice, by using organic solvents. If tion of polyurethane resins from aqueous polyurethane one wishes to emulsify prepolymers containing free NCO dispersions. 30 groups with the use of emulsifiers it is advantageous to For example, prepolymers with terminal reactive iso use hydrocarbons which are left in the latex. In the case cyanate groups obtained by reacting compounds which of dispersions of polyurethane polyelectrolytes, the low have active hydrogen atoms with a stoichiometric excess boiling solvent used for the preparation of the dispersion of diisocyanates may be dissolved in an organic solvent is removed from the dispersion by distillation and re and emulsified with the aid of emulsifiers under the action 35 turned to the cycle. Although the dispersions are com of powerful shearing forces in water or in solutions of pletely free from organic solvents when applied, this meth diamines in water (German Auslegeschrift No. 1,097 od of preparation is economically less satisfactory. 678) (U.S. 2,968,575, Mallonee). In this process, an emul It is therefore an object of this invention to provide sion of the reactive prepolymer is first produced. A chain improved polyurethane polymers. It is another object to lengthening reaction then takes place as a result of the dif 40 provide improved polyurethane dispersions. It is another fusion of water or diamine into the droplets of the emul object to provide aqueous polyurethane dispersions with sion and reaction with the isocyanate groups occurs so out the necessity of using solvents. It is still another ob that, finally, dispersed particles of polymeric polyurethane ject of this invention to provide polyurethane polymers ureas are formed. This process has the disadvantage that from dispersions that are useful in all types of applica it is difficult to influence and control the chain lengthening 45 tions. reaction because it takes place in the droplets of emulsion The foregoing objects and others which will become ap and, as is well known, the chain lengthening reaction of parent from the following description are accomplished polyisocyanates with water or diamines proceeds with in accordance with this invention, generally speaking, by considerable chain branching. In addition, the dispersions providing polyurethanes by dispersing methylol-contain obtained are not stable for any length of time. 50 ing, solid or liquid, relatively low molecular weight poly These disadvantages can be partly avoided by a con urethane polyelectrolytes in water and then effecting fur tinuous method of preparation in which the emulsification ther chain lengthening. This can be done by heat treat of the prepolymer is carried out at a low temperature ment, before and/or during and/or after removal of the and the diamine is added subsequently. Even by this varia water via methylene bridges. According to a particular tion of the process, however, relatively coarse dispersions 55 embodiment of the process, the polyurethanes to be dis which tend to sediment out or coagulate are obtained, and persed contain reactive terminal groups which are partic the resulting coatings, films and impregnations have very , ularly reactive with formaldehyde. These groups are re little resistance to water. It has not so far been possible acted with formaldehyde in the presence of water during to produce, by such a process, latices with particles be or immediately before dispersion. According to another low 400 mu, which would dry at room temperature or, at 60 embodiment of the process, the polyurethanes which are least, at temperatures below 80° C. to form coatings with to be dispersed are reacted, e.g., via isocyanate groups, satisfactory properties rendering them useful. In addition, with compounds which contain reactive methylol groups, coarsely disperse, sedimenting but redispersible dispersions so that polyurethanes with terminal free methylol groups cannot be produced by this process. are formed. Contrary to expectations, premature cross Furthermore, numerous processes are known for pro 65 linking does not occur; on the contrary, the process of ducing emulsifier-free polyurethane dispersions by incor dispersion is considerably facilitated by the addition of porating cationic or anionic salt groups into the polyure formaldehyde and the terminal methylol groups. Chain thane polymer chains and mixing solutions of such poly lengthening to produce the high molecular weight poly urethanes in organic solvents with water. Stable aqueous urethane thus takes place during and after the dispersion. polyurethane dispersions are obtained after removal of 70 A person skilled in the art would not have expected the organic solvent by distillation. that the preparation of aqueous polyurethane dispersions, It has also been proposed to disperse such ionic poly in other words a colloidal two-phase system would be 3,756,992 3 4. possible according to the invention without the aid of (1) has an average molecular weight of less than about (1) emulsifiers, (2) dispersing apparatuses such as high 25,000, preferably about 2,000 to about 10,000, speed stirrers or other apparatuses which produce shear (2) contains hydrophobic nonionic chain segments of at ing forces, (3) solvents, since, according to the state of least 60 chain links, the art, at least one of these aids is necessary, and that (3) contains 4 to 120 millieduivalents percent, preferably one can obtain, e.g., hydrophobic coatings from the re 8 to 80 milliequivalents percent of salt groups or of sulting dispersions. groups which are capable of salt formation which are This invention thus relates to a process for the prepara converted into salt groups in the course of the process, tion of polyurethanes which is characterized in that solid (4) has a viscosity of less than 1,500 poises and pref or liquid polyurethane polyelectrolytes which contain O erably 50 to 1,000 poises at 120° C. and methylol groups are dispersed by mixing them with water, (5) contains terminal acylated amino groups of the gen and the dispersed poyurethane polyelectrolytes are Sub eral formula jected to heat treatment at 25 to 200° C. before and/or -X-NHR during and/or after removal of the water. According to the invention, higher molecular weight which are reactive with formaldehyde, polyurethane polyelectrolytes are preferably used. By in which formula: "polyurethane polyelectrolytes' is meant compounds hav X represents -CO-, -CS-, -SO2-, ing terminal reactive methylol groups and which have been obtained from higher molecular weight polyiso -NR-CO cyanates and methylol compounds, and which have: -NR-CS-, -O-CO-, -S-CO-, -O-CS-, -O-SO-, -CNR-, -NR-CNR-, (1) an average molecular weight of less than about -CO-NR-CO 25,000, preferably about 2,000 to about 10,000, (2) hydrophobic nonionic chain segments of at least 60 -CS-NR-CS chain links, (3) 4 to 120 millieauivalents percent, preferably 8 to 80 millieduivalents of salt groups or of groups which are capable of salt formation and which are converted into salt groups in the course of the process, and (4) a viscosity of less than about 1,500 and preferably 30 'i about 100 to about 1,000 poises at 120° C. The polyurethane electrolyte is dispersed with water at to ?il, about 20 to about 150° C., preferably at about 50 to about 130 C, the quantity of water being from about and 0.5 to about 4 times the quantity of polyurethane poly Z represents electrolyte. The polyurethane electrolyte is then subjected to a heat treatment at about 25 to about 200 C., pref R erably about 70 to about 150° C. before and/or during and/or after removal of the water. 40 -NHR, -( ) or R Particularly suitable compounds with reactive methylol and groups are amine-formaldehyde resins or phenol-form R. preferably denotes a hydrogen atom or an alkyl aldehyde resins with free methylol groups. radical or an alkenyl radical which has 1 to 4 carbon It is also advantageous to adjust the polyurethane dis atoms and which may also be part of a heterocyclic 5 persions to a pH between 4 and 2 before, during or after 45 membered or 6-membered ring with 1 to 3 heteroatoms, the heat treatment. and which may be substituted by OH, OCH, OCH5, In one preferred embodiment of the invention, the poly CCl3, COOH, or SOH, or R denotes CN, CO-R', urethane polyelectrolyte which contains methylol groups SO-R' (in which R' represents an alkyl, alkenyl, alkoxy is prpared during or immediately before dispersion, by or carboxyl radical with 1 to 4 carbon atoms), by the the reaction between an aqueous formaldehyde solution 50 reaction therewith of aqueous formaldehyde-containing and a polyurethane polyelectrolyte which contains acyl solutions at temperatures above about 50° C., preferably ated amino groups which are reactive with formaldehyde. about 80 to about 150° C., the equivalent ratio of In one particularly suitable embodiment of the inven -X-NHR to formaldehyde being between 1:0.3 and 1:4 tion, the polyurethane polyelectrolyte which contains and the quantity of water amounting to about 0.5 to about methylol groups is prepared by the action of a form 55 4 times the quantity of polyurethane. aldehyde-containing aqueous solution at temperatures In this process, the reaction with the aqueous solution above about 50° C. on a poyurethane polyelectrolyte which contains formaldehyde should preferably take place which has been obtained from compounds with reactive at pH values between 9 and 4.1. The acylated amino hydrogen atoms and a molecular weight of about 50 to group -X-NHR is advantageously an unsubstituted about 20,000 and polyisocyanates and which contains at 60 -CO-NH2 group or an unsubstituted urea or biuret least 4 millieduivalents percent of salt groups or groups group -NH-CO-NH2. Polyurethane electrolytes which are capable of salt formation and which are con which contain groups which are reactive with formalde verted into salt groups in the course of the process, as hyde may also advantageously be prepared by the addi well as terminal acylated amino groups which are reac tion of compounds which contain (potential) salt groups tive with formaldehyde. 65 S. Plyurethanes which contain reactive olefinic double According to the invention it is also especially advan OCS. tageous to use, in a further embodiment of the invention, Those polyurethane polyelectrolytes which contain at a polyurethane polyelectrolyte which contains methylol least one of the following groups: groups which has been prepared from a (potential) poly urethane polyelectrolyte which is free from NCO groups -jo- -to- --- -COO (-) -SO(-) --O-SO(-) and which has been obtained from compounds which O(-) contain reactive hydrogen atoms and have a molecular / weight of about 50 to about 20,000, preferably about 50 -SO(-) RN (R-Falkyl, cycloalkyl, aralkyl, aryly to about 8,000, and polyisocyanates, and which R 3,756,992 5 6 are particularly suitable for use in the present invention. dimethylmethane (bis - hydroxyethyldiane), and succinic In further embodiments of the present invention the poly acid, glutaric acid, adipic acid, suberic acid, phthalic urethane dispersions are adjusted to a pH of between 4.2 acid, isophthalic acid, terephthalic acid, dimethyl tereph and 2 before, during or after the heat treatment, or 0.5-20 thalate, terephthalic acid bis-glycol ester, maleic acid an percent by weight of polyisocyanate of molecular weight hydride, fumaric acid, 6-hydroxy caproic acid, 4-hydroxy 110-4,000 are incorporated in the dispersions by emul benzoic acid and trimellitic acid. sification after the addition of at least half the total Polyhydroxyl compounds which already contain ure amount of water. thane or urea groups as well as natural polyols which Dispersion, within the context of this invention, are may or may not be modified, such as castor oil, or car heterogeneous two-phase water/polyurethane systems in IO bohydrates may also be used. general, especially those in which water forms the con In principle, polyhydroxyl compounds which contain tinuous phase. The term also covers sedimenting suspen basic nitrogen atoms, e.g. polyalkoxylated primary amines sions with particle diameters above approximately 5 mu, or polyesters or polythioethers in which an alkyl dietha as well as colloidal solutions or sols with particle diam nolamine has been incorporated by condensation may eters of about 10 to 100u. The term does not, however, also be used. Compounds which contain reactive halo include optically clear, homogeneous aqueous solutions. gen atoms may also be incorporated by condensation, Compounds containing several reactive hydrogen atoms e.g. glycerol-o'-chlorohydrin. Such compounds may also which are suitable for use in the preparation of the poly be in the alkylated or onium form. Polyesters with built urethane polyelectrolytes for use according to the inven in sulphonate or carboxylate groups such as those de tion are linear or branched and have a molecular weight 20 scribed, for example, in French patent specification No. of 50-20,000, preferably 50-8,000. These compounds 1,496,584 may be used. Of those polymers and copoly which are known per se have terminal hydroxyl, carboxyl, mers of vinyl compounds which contain more than one amino or mercapto groups. Especially advantageous higher hydroxyl group, those which have a molecular weight of molecular weight compounds within this class of com 500 to 20,000 and contain 2 to 10 hydroxyl groups are pounds are polyhydroxyl compounds such as polyesters, 25 preferably used. Examples of these are partially saponi polyacetals, polyethers, polythioethers, polyamides and fied vinyl acetate copolymers, low molecular weight poly polyester amides, and those vinyl polymers which have butadienes which have OH groups and, above all, ox more than one hydroxyl group. idized polyethylene or polypropylene, the method of prep Suitable polyethers are, for example, the polymeriza aration of which has been described, for example, in tion products of styrol oxide, ethylene oxide, propylene 30 British patent specification No. 959,362. oxide, tetrahydrofuran, butylene oxide, epichlorohydrin In order to vary the lyophilic or hydrophobic proper and their copolymerization or graft polymerization prod ties and the mechanical properties of the products of the ucts as well as the polyethers obtained by condensation process, mixtures of different polyhydroxyl compounds of polyhydric alcohols or mixtures thereof and the poly may be used. Suitable higher molecular weight com ethers obtained by alkoxylation of polyhydric alcohols, pounds which have amino end groups have been de amines, polyamines and amino alcohols. Isotactic poly scribed, for example, in French patent specification Nos. propylene glycol may also be used. Products which have 1,361,810 and 1,300,981, German Auslegeschrift No. a high ethylene oxide content are not suitable if they 1,122,254 and United States patent specification No. lead to the formation of water-soluble polyurethanes. 2,888,439. Suitable polyacetals are, for example, those polyacetals 40 One may use any aromatic and aliphatic diisocyanates, which can be prepared from such glycols as diethylene such as 1,5-naphthylene diisocyanate as starting mate glycol, triethylene glycol, and 4,4'-dihydroxy-diphenyl-di rials for the preparation of the polyurethane polyelec methylmethane, hexane diol, and formaldehyde. Suitable trolytes used according to the invention. These com polyacetals can also be prepared by polymerization of pounds include cyclic acetals. 45 4,4'-diphenylmethane diisocyanate; Particularly useful polythioethers are the condensations, 4,4'-diphenyl dimethyl methane diisocyanate; products of thiodiglycol with itself and/or with other di- and tetra-alkyldiphenylmethane diisocyanates; glycols, dicarboxylic acids, formaldehyde, aminocarbox 4,4'-dibenzyl diisocyanate; ylic acids or aminoalcohols. Depending upon the co-con 1,3-phenylene diisocyanate; ponent used the products are polythioethers, polythio 50 1,4-phenylene diisocyanate; mixed ethers, polythioether esters or polythioether ester the isomers of touylene diisocyanate, if desired mixtures amides. Polyhydroxyl compounds of this type can also thereof; be used in alkylated form or in mixture with alkylating 1-methyl-2,4-diisocyanatocyclohexane; agents. 1,6-diisocyanate-2,2,4-trimethylhexane; Other polyesters, polyester amides and polyamides which 1,6-diisocyanato-2,4,4-trimethylhexane; may be used are the predominantly linear or branched 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl condensates obtained from polyvalent saturated and un cyclohexane; saturated alcohols, amino alcohols, diamines, polyamines chlorinated and brominated diisocyanates; and mixtures thereof, e.g. polyester terephthalates or poly phosphorus-containing diisocyanates; carbonates. Polyesters obtained from lactones, e.g. e-cap 60 4,4'-diisocyanatophenylperfluoroethane; rolactone, or from hydroxycarboxylic acids, may also be tetramethoxy-butane-1,4-diisocyanate; used. The polyesters may have terminal hydroxyl or butane-1,4-diisocyanate; carboxyl groups. The alcohol components used in their hexane-1,6-diisocyanate; synthesis may also consist entirely or partly of higher dicyclohexyl methane-diisocyanate; molecular weight polymers or condensates such as poly 65 ethers, polyacetals or polyoxymethylenes. Unsaturated cyclohexane-1,4-diisocyanate; polyesters may be grafted with vinyl monomers. ethylene diisocyanate; The following are especially suitable components for p-xylylene diisocyanate and use in the synthesis of polyesters: ethylene glycol, dieth m-xylylene diisocyanate. ylene glycol, triethylene glycol, tetraethylene glycol, 1,2- O One may use the hydrogenation products of the above propylene glycol, 1,3-propylene glycol, 2,3-butane diol, mentioned aromatic diisocyanates. Uurethane- and biuret 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 2,2- di- or tri-isocyanates may also be used, e.g. adducts of dimethyl-1,3-propane diol, cyclohexane dimethanol, quini 1,6-hexane diisocyanate. 1,3-xylylene diisocyanate or 1 tol, glycerol, trimethylol propane, hexane triol, pentaeryth methyl-2,4-di - isocyanato - cyclohexane with water or ritol, butene diol and 4,4'-bis-3-hydroxyethoxy-diphenyl 5 amines or polyalcohols. One may also use isocyanates 3,756,992 7 8 which contain ionic groups, such as those obtained, for and B-alanine, 6-aminocaproic acid, 4-aminobutyric acid, example, by the addition of isocyanates with reactive the isomeric mono- and diamino-benzoic acids, and the halogen atoms to di- or polytertiary amines, bis-isocy isomeric mono- and diaminonaptholic acids as well as anatoethyl phthalate, polyisocyanates which have reac talkyesters thereof. tive halogen atoms, such as 1-chloromethylphenyl-2,4- (5) Water. diisocyanate, 1-bromoethylphenyl-2,6-diisocyanate, and 3, Less common chain lengthening agents, e.g. high melt 3-bis-chloromethylether-4,4'-diphenylisocyanate. Suitable ing chain lengthening agents with reactive hydrogen atoms polyisocyanates which contain sulphur are obtained, for are also suitable for use in the present invention, C.9. example, by reacting 2 mols of hexamethylene diisocy 4,4'-di-(N-methyl-6-hydroxyethylamino)- anate with 1 mol of thiodiglycol or dihydroxydihexyl O sulphide. Triisocyanates or crude commercial mixtures diphenylmethane, of polyisocyanates may also be used. Of special inter ethyl-bis-3-hydroxy-cyclohexyl-phosphine oxide, est are partly masked polyisocyanates, e.g. dimeric touyl N,N-dimethyl-ethylenediamine, oxalamidrazone, ene diisocyanate, or polyisocyanates which have been oxalic2,6-di-(hydroxymethyl)-tetrahydropyran, acid bis-ethanolamide, partly reacted with, for example, phenol, tertiary buta di-(hydroxy-neopentylidene)-pentaerythritol, nol, phthalimide, caprolactam or methylethyl ketoxime. dimethylol tetrahydropyrimidinethione, Aliphatic and araliphatic diisocyanates are especially N,N'-bis-(2-aminoethyl) oxalic acid amide, preferred. Mixtures of different isocyanates may be suit N,N'-bis-(2-aminopropyl)-oxalic acid amide, able. dihydroxydiethyl sulphone, The low molecular weight compounds with reactive 4-methylamino-butanol-(2), hydrogen atoms which may be used in the preparation of N,N'-carboxybutylurea, the polyurethane electrolytes used according to the inven methylene-bis-benzoic acid, tion include the following compounds: methylene-bis-benzyl alcohol, (1) The usual saturated unsaturated glycols such as hexane-bis-semicarbazide, ethylene glycol or condensates of ethylene glycol; butane 25 y-hydroxybutyric acid hydrazide, diol-1,3-; butanediol-1,4; butenediol; propanediol-1,2; pro 6-aminocaproic acid hydrazide, panediol-1,3; neopentyl glycol, hexanediol; bishydroxy phenyl glycol, methylcyclohexane; 1,4-bis-(3-hydroxyethoxy benzene; 4, dimethyloldihydropyran, 4'-bis-hydroxyethoxy-diphenyl-dimethylmethane, bis-gly dimethyloltetrahydrofuran, col terephthalate; succinic acid dig-hydroxyethylamide; 30 succinic acid di-IN-methyl-(6-hydroxyethyl)-amide; 1,4- tetrachlorobutane diol, di(g - hydroxy-methyl-mercapto)-2,3,5,6-tetrachloroben dithiooxamide, Zene; 2-methylidenepropanediol-(1,3) and 2-methylpro pentaerythritol-mono-acetone ketal, panediol-(1,3). pentachlorophenyl glycerol ether, (2) Aliphatic, cycloaliphatic and aromatic diamines 1,4-dipiperazino-butane-2,3-diol, such as ethylene diamine, hexamethylene diamine, 1,4-cy sulphuryl disulphamide, clohexylene diamine, benzidine, diamino-diphenylmeth 1,1-(di-hydroxymethyl)-A3-cyclohexene, ane, dichloro-diamino-diphenylmethane, the isomers of lauric acid di-(hydroxyethyl)-amide, phenylene-diamine, hydrazine, ammonia, carbohydrazide, isobutylenediureide, adipic acid dihydrazide, sebacic acid dihydrazide, pipera 40 and the following compounds: HOOC-C-NH-CO-C o-NH-( >-so-g X-NHC O-CO-NH-CH-COOH Cs

HOOC-CH-NH-CO-C roto-O O-CO-NH-CH-COOH

CHs CBIs CH CH Ho-CH-i-C 0-0-CH-)-CH-OH Ho-CH-b-c O-NH-CH-C-CH-OH H &H, H

CH 3 HO-(CH2)-NH-CO-C "O POr O-CO-NH-(CH)-OH

HO-(CH)-NH-CO-CO-N -Y-Co-c O-NH-CH-CH-OH zine, N-methyl-propylenediamine, 4,4'-diaminodiphenyl When such chain lengthening agents which are strongly sulphone, 4,4'-diaminodiphenyl ether, 4,4'-diamino-di polar and capable of forming hydrogen bridge bonds are phenyldimethylmethane and 2,4-diamino-6-phenyltriazine. used in combination with ionic chain lengthening agents 70 Such as those formed by salt formation of basic chain (3) Aminoalcohols such as ethanolamine, propanola lengthening agents, they yield products of exceptionally mine, butanolamine, N-methylethanolamine and N-meth high strength and water resistance even under the action yl-isopropanolamine. of moisture and solvents. (4) Aliphatic, cycloaliphatic, aromatic and heterocyclic Chain lengthening agents with at least one basic nitro mono- and diamino-carboxylic acids such as glycine, c 75 gen atom are, for example, mono-, bis- or polyalkoxylated 3,756,992 10 aliphatic, cycloaliphatic, aromatic or heterocyclic primary N,N-dimethylethylenediamine, amines Such as 1-diethylamino-4-aminopentane, N-methyldiethanolamine, o-aminopyridine, N-ethyldiethanolamine, 3-amino-N-ethyl carbazol, N-propyl-diethanolamine, N,N-dimethylpropylene diamine, N-isopropyl-diethanolamine, N-amino-propyl-piperidine, N-butyl-diethanolamine, N-aminopropylmorpholine, N-isobutyl-diethanolamine, N-aminopropyl-ethylene-imine and N-olleyl-diethanolamine, 1,3-bispiperidino-2-aminopropane. N-stearyl-diethanolamine, 10 Different chain lengthening agents may be used in com hydroxyethylated amines of coconut oil, bination. N-allyl-diethanolamine, The following compounds are examples of monofunc N-methyl-diisopropanolamine, tional alkylating agents which may be used for converting N-ethyl-diisopropanolamine, the basic reactants into the salt form when preparing the N-propyl-diisopropanolamine, polyurethane polyelectrolytes: methyl chloride, methyl N-butyl-diisopropanolamine, bromide, methyl iodide, ethyl bromide, propyl bromide, N-cyclohexyl-diisopropanolamine, butyl bromide, dimethylsulphate, diethyl sulphate, methyl N,N-dihydroxyethyl aniline, chloromethyl ether, methyl 1,2-dichloroethyl ether, ethyl N,N-dihydroxyethyl-toluidine, chloromethyl ether, benzyl chloride, benzyl bromide, p N,N-dihydroxyethyl-a-aminopyridine, 20 chlorobenzyl chloride, trichlorobenzyl chloride, p-nitro N,N'-dihydroxyethyl-piperazine, benzyl chloride, ethylene chlorohydrin, ethylene bromo dimethyl-bis-hydroxyethylhydrazine, hydrin, epichlorohydrin, ethylene oxyde, propylene oxyde, N,N'-bis-(6-hydroxy-ethyl)-N,N'-diethylhexahydro-p- styrene oxyde, benzene-, toluene-, naphthalene-sulphonic phenylene-diamine, acid esters, co-bromoacetophenone, dinitrochlorobenzene, N-3-hydroxyethyl piperazine and 8-chloropenteneamide, chloroacetic acid and its ester and amides, chloromethyl-dimethyl-ethoxysilane, pentamethyl polyalkoxylated amines such as hydroxypropylated meth chloromethyl-disiloxane, pentamethyl-bromomethyl-di yl-diethanolamine. One may also use, for this purpose, siloxane, glycol monobromoacetic acid ester, glycerol compounds such as monochloracetic acid ester, bromoethyl isocyanate, N-methyl-N,N-bis-y-aminopropylamine, 30 chloromethyl naphthalene, 3-methyl-3-hydroxymethyl N-(y-aminopropyl)-N,N'-di-methylethylene diamine, oxetane methane sulphonate, phenylethylbromide, p-2- N-(y-aminopropyl)-N-methyl-ethanolamine, bromoethyl benzoic acid, 5-chloromethyl-furan-2-car N,N'-bis-(y-aminopropyl)-N,N'-dimethylethylenediamine, boxylic acid, ethyl phosphonous acid dichloroisopropyl N,N'-bis-(y-amino-propyl)piperazine, ester, bromoethyl acetoacetate, 1,3-propane Sultone, 1,4- N-((3-aminoethyl)-piperazine N,N'-bis-hydroxyethyl butane sultone. Additional examples of these compounds propylene diamine, may be found in German Auslegeschrift No. 1,205,087. 2,6-diaminopyridine, Quaternizations may also be carried out with cyanogen diethanolamino acetamide, chloride or cyanogen bromide. Epoxies may be used in di-ethanolaminopropionamide, combination with water and/or an acid as quaternizing N,N'-bis-hydroxyethyl-phenyl-thiosemicarbazide, 40 agents: N,N-bis-hydroxyethyl-methylsemicarbazide, Polyfunctional alkylating agents are also suitable, e.g. p,p'-bis-aminomethyl-dibenzyl-methylamine and 1,4-dibromobutane, p-xylylene dichloride, 1,3-dimethyl 2,6-diaminopyridine. 4,6-bis-chloromethyl benzene, methylene bis-chloroacet amide, hexa-methylene-bis-bromoethyl urethane and ad Suitable chain lengthening agents with quaternizable 45 ducts of 2-3 mols of chloroacetamide with di- or triso halogen atoms or R-SOO groups are, for example, glyc cyanate. Other suitable polyfunctional alkylating agents erol-a-chlorohydrin, glycerol monotosylate, pentaerythri are given in, for example, published Dutch patent ap tol-bis-benzene sulphate, glycerol monomethane-sulpho plication No. 67/03743. nate, adducts of diethanolamine and chloromethylated Examples of tertiary amines which may be used in the aromatic isocyanates or aliphatic halogen isocyanates, 50 quaternization reaction are trimethylamine, triethylamine, such as N,N-bis-hydroxyethyl-N'-m-chloromethylphenyl triethanolamine, dimethylaminoethanol, N-methyl-di urea, N-hydroxyethyl-N'-chlorohexyl urea, glycerolmono ethanolamine, pyridine, quinoline and N-dimethylamino chloroethylurethane, bromoacetyl dipropylene triamine, propyl-diethanolamine. and chloroacetic acid diethanolamide. One may also use, at this stage of the reaction for the Tri- or higher functional components may be used, e.g. salt formation, various acids including those which, at branched polyesters or polyethers, tri- or higher functional the same time, have a chain lengthening function, e.g. isocyanates such as tris-isocyanatohexyl biuret or cyclic sulphurous acid, sulphuric acid, hypophosphorous acid, isocyanurate oligomers of diisocyanates. Higher functional phosphinic acids, phosphonous acids and phosphonic chain lengthening agents such as glycerol, trimethylol pro acids, glycollic acids, lactic acid, succinic acid, tartaric pane, pentaerythritol, dipropylene triamine, hexane triol 60 acid, oxalic acid, phthalic acid and trimellitic acid. or triethanolamine may also be used. Other suitable acids are mentioned in German patent Monofunctional compounds which have only one group specifications Nos. 1,178,586 and 1,179,363. Particularly that is reactive with isocyanates may also be included, advantageous acids are those which greatly increase the e.g. (un) saturated fatty alcohols, fatty amines or fatty hydrophilic character and, in particular, the dispersibility acids, resinic acids, 65 of the polyurethanes, such as hydrochloric acid, fluoboric acid, amidosulphonic acid, phosphoric acid and their N,N-dimethylethanolamine derivatives, tartaric acid, oxalic acid, lactic acid, acetic N,N-diethylethanolamine, acid and acrylic acid. Various salt-forming agents may 1-dimethylaminopropanol-(2), also be used in combination therewith. A synergistic ef N-hydroxyethylmorpholine, 70 N-methyl-N-3-hydroxyethyl aniline, bility.fect is thereby achieved in connection with the dispersi N-hydroxyethyl piperidine, Insofar as the compounds with reactive hydrogen atoms ox-hydroxyethyl pyridine, hitherto mentioned contain basic nitrogen atoms or di ?y-hydroxyethyl quinoline, valent sulphur atoms, in combination with alkylating N,N-dimethyl hydrazine, 75 agents or acids, they serve for the formation of cationic 3,756,992 1. 12 polyurethane polyelectrolytes. Accordingly, cationic poly naphthylamine-(1)-sulphonic acid, urethane polyelectrolytes can be prepared from com naphthylamine-(2)-sulphonic acid, pounds with reactive hydrogen atoms, reactive halogen naphthylamine disulphonic acids, atoms or ester groups of strong acids in combination with naphthylamine trisulfonic acids, tertiary, secondary or primary amines, organic sulphides 5 4,4'-di-(p-aminobenzoyl-amino) diphenyl urea disulphonic or phosphines. acid-(3,3'), The polyurethanes can also be correspondingly modi phenyl hydrazine disulphonic acid-(2,5), fied anionically by the incorporation of suitable com 2,3-dimethyl-4-aminobenzene disulphonic acid-(4,5), pounds. Suitable starting compounds for the preparation 4'-aminostilbene disulphonic acid-(2,2)-(4-azo-4)- of these polyurethane polyelectrolytes are compounds IO anisole, which have at least one hydrogen atom which will react carbazole disulphonic acid-(2,7), with isocyanate groups and at least one anionic salt type taurine, group which is capable of anionic salt formation or if methyltaurine, desired mixtures thereof: butyl taurine, (1) Hydroxy acids and mercapto acids such as 3-amino-benzoic acid-(1)-sulphonic acid-(5), glyceric acid, glycollic acid, thioglycollic acid, lactic acid, 3-aminotoluene-N-methane-Sulphonic acid, trichlorolactic acid, malic acid, dihydroxymalic acid, di 6-nitro-1,3-dimethylbenzene-4-sulphamic acid, hydroxyfumaric acid, tartaric acid, dihydroxy tartaric 4,6-diaminobenzene disulphonic acid-(1,3), acid, mucic acid, saccharic acid, citric acid, glyceroboric 2,4-diaminotoluene Sulphonic acid-(5), acid, pentaerythritol-boric acid, mannito-boric acid, 20 4,4'-diaminodiphenyl-disulphonic acid-(2,2'), Salicylic acid, 2,6-dihydroxybenzoic acid, protocateculic 2-aminophenolsulphonic acid-(4), acid, ox-resorcylic acid, B-resorcylic acid, hydroquinone 4,4'-diamino-diphenylether-sulphonic acid-(2), 2,5-dicarboxylic acid, 4-hydroxyisophthalic acid, 4,6-di 2-aminoanisole-N-methane sulphonic acid, hydroxyisophthalic acid, hydroxyterephthalic acid, 5,6,7, 2-amino-diphenylamino-sulphonic acid, 8-tetrahydro-naphthal-(2)-carboxylic acid-(3), 1-hy droxynaphthoic acid-(2)-carboxylic acid-(3), 1-hydroxy ethylene glycol sulphonic acid and naphthoic acid-(2), 2,8-dihydroxynaphthoic acid-(3), B 2,4-diaminobenzene sulphonic acid; hydroxypropionic acid, m-hydroxybenzoic acid, pyrazo (6) Organo phosphorous compounds such as deriva lone carboxylic acid, uric acid, barbituric acid and 2,6- tives of phosphinic acid, phosphonous acids, phosphonic bis-hydroxymethyl-p-cresol, tris - hydroxymethyl-acetic 30 acids and phosphoric acids as well as the esters of phos acid, c, ox-bis-hydroxymethyl-propionic acid, a,c-bis-hy phorous acid and of phosphoric acid and their thioana droxymethyl-butyric acid. logues, e.g. bis-(o-hydroxyisopropyl)phosphinic acid hy (2) Aliphatic, cycloaliphatic, aromatic and hetero droxyalkane phosphonic acid, phosphorous acid bis-glycol cyclic mono- and diaminocarboxylic acids such as glycine, ester, phosphorous acid bis-propylene glycolester, phos a- and B-alanine, 6-aminocaproic acid, 4-aminobutyric phoric acid, phosphoric acid bis-ethylene glycol ester and acid, sarcosine, methionine, leucine, isoleucine, serine, phosphoric acid bis-propylene glycol ester; valine, ornithine, histidine, lysine, proline, phenylalanine, (7) Furthermore, one may use as hydroxy-, mercapto threonine, cystein, asparagine, glutamine, arginine, as and aminocarboxylic acids and sulphonic acids, polycar partic acid, glutamic acid, oxaluric acid, anilidoacetic boxylic acids and polysulphonic acids, the (saponified) acid, anthranilic acid, 2-ethylaminobenzoic acid, 3-amino 40 products of unsaturated acids such as acrylic acid, meth benzoic acid, 4-aminobenzoic acid, N-phenylaminoacetic acrylic acid and unsaturated nitrile such as acrylonitrile; acid, 3,4-diaminobenzoic acid and 5-aminobenzene dicar of cyclic dicarboxylic acid anhydrides such as maleic acid boxylic acid. anhydride, phthalic acid anhydride and succinic acid an (3) Aliphatic, cycloaliphatic, aromatic and hetero hydride; of Sulphocarboxylic acid anhydrides such as cyclic di- and polycarboxylic acid such as oxalic acid, the anhydride of sulphoacetic acid and of o-sulphobenzoic malonic acid, succinic acid, glutaric acid, adipic acid, acid; of lactones such as (3-propiolactone and y-butyro pimelic acid, suberic acid, azelaic acid, sebacic acid, the lactone, the addition products of the reaction products of isomeric phthalic acids, diphenic acids, the isomeric olefines with sulphur trioxide, such as carbyl sulphate; naphthalic acids, maleic acid, thiodiglycollic acid, fumaric of epoxycarboxylic and epoxysulphonic acids such as acid, sulphodiacetic acid, diglycollic acid, methylene-bis 50 glycidic acid and 2,3-epoxypropane sulphonic acid, of thioglycollic acid, the isomeric pyridinocarboxylic acids, Sultones such as 1,3-propane sultone, 1,4-butane sultone the isomeric quinoline dicarboxylic acids, citric acid, and 1,8-naphthoSultone or of disulphonic acid anhydrides ethylene diaminotetracetic acid and nitrilotriacetic acid; Such as benzene disulphonic acid-(1,2) anhydride with (4) Hydroxy- and carboxy-Sulphonc acids: 2-hydroxy aliphatic and aromatic amines such as 1,2-ethylene di ethane sulphonic acid, phenolsulphonic acid-(2), phenol 55 amine, 1,6-hexamethylene diamine, the isomeric phenyl sulphonic acid-(3), phenolsulphonic acid-(4), phenoldi ene diamines, diethylene triamine, triethylene tetramine, sulphonic acid-(2,4), sulphoacetic acid, m-sulphobenzoic tetraethylene pentamine, pentaethylene hexamine, hydra acid, p-sulphobenzoic acid, benzoic acid-(1)-disulphonic zines or alkylated hydrazines, ammonia, amino alcohols acid-(3,5), 2-chlorobenzoic acid -(1)-sulphonic acid-(4), such as the hydroxyalkylated amines and hydrazines, for 2-hydroxybenzoic acid-(1)-sulphonic acid-(5), naphthol 60 example compounds such as ethanolamine, diethanol (1)-sulphonic acids, naphthol-(1)-disulphonic acids, 8 amine, triethanolamine, ethanol ethylenediamine and eth chloronaphthol-(1)-disulphonic acid, naphthol-(1)-tri anol hydrazine; alcohols such as ethylene glycol, propyl sulphonic-acids, naphthol - (2) - sulphonic acid-(1), ene glycol, 1,3- and 1,4-butane diol, 1,6-hexane diol; poly naphthol-(2)-trisulphonic acids; 1,7-dihydroxynaphthal hydric alcohols such as trimethylol propane, glycerol and enesulphonic acid-(3), 1,8-dihydroxynaphthalenedisul hexane triol; the addition products (which may be hy phonic acid-(2,4), chromotropic acid, 2-hydroxy drogenated), of epoxy and ethylene imine compounds naphthoic acid-(3)-sulphonic acid-(6) and 2-hydroxy such as ethylene oxide, propylene oxyde, butylene oxyde, carbazol-sulphonic acid-(7); styrene oxide and ethylene imine, and unsaturated ni (5) Aminosulphonic acids: Amidosulphonic acid, hy triles such as acrylonitrile with aliphatic and aromatic droxylamine-monosulphonic acid, hydrazine disulphonic 70 aminocarboxylic acids and aminosulphonic acids; the re acid, sulphanilic acid, action products of hydroxyalkane Sulphonic acids, halo N-phenylaminomethanesulphonic acid, genated carboxylic and sulphonic acids with optionally 4,6-dichloroaniline sulphonic acid-(2), alkylated hydrazines such as hydrazine acetic acid, hydra phenylene diamine-(1,3)-disulphonic acid-(4,6), zine ethane sulphonic acid and hydrazine methane sul N-acetyl-naphthylamine-(1)-sulphonic acid-(3), 5 phonic acid; the saponified addition products of cyano 13 3,756,992 14 hydrins with hydrazine such as 1,2-hydrazine-bis-isobuty anhydrides, disulphonic acid anhydrides, sulphocarboxylic ric acid; furthermore one may use the addition products acid anhydrides, sultones, lactones, epoxycarboxylic acids, of sodium hydrogen sulphite with olefinically unsaturated epoxysulphonic acids, N-carboxyglycine anhydride, carby compounds such as allyl alcohol, maleic acid, maleic acid sulphate. This method of modification has been fully de bis-ethylene- and bis-propylene-glycol ester; scribed in German Auslegeschrift No. 1,237,306. The (8). Hydrazine carboxylic acids such as hydrazine di processes described in Belgian patent specifications Nos. carboxylic acids. v. 636,799 and 658,026 may also be used for the production (9) Higher molecular weight condensates such as poly of cationic polyurethanes which may be used as starting esters which contain carboxyl groups. material for the process according to the present inven The following are examples of compounds which are O tion. suitable for conversion into the salt form for use in the The sequence in which the components used for syn preparation of anionic polyurethane polyelectrolytes: thesizing the polyurethane polyelectrolytes are added is, in ... (1) Organic bases such as monofunctional primary, principle, immaterial. One may, for example, mix all the secondary and tertiary amines, for example, methylamine, components together at room temperature or elevated diethylamine, triethylamine, trimethylamine, dimethyl 5 temperature, including the component which carries at amine, ethylamine, tributylamine, pyridine, aniline, tolu least one acylated amino group, which component is to be idine, alkoxylated amines such as ethanolamine, dietha described in more detail below, or the di- or polymethylol nolamine, triethanolamine, methyldiethanolamine, di compound, and then let all these components react to methylamine ethanol, oleyl diethanolamine and polyfunc gether, in which case the reaction mixture usually has to be tional polyamines in which the individual amino groups 20 heated to about 100-160° C. However, if a basic compo may differ in basicity, e.g. the polyamines obtained by nent or a catalyst is present, the reaction usually takes hydrogenation of addition products of acrylonitrile with place spontaneously. Alternatively one may first prepare primary and secondary amines or peralkylated or partial an NCO-containing prepolymer in known manner and ly alkylated polyamines such as N,N-dimethylethylene di then react this. In one especially preferred method, the amine; furthermore, one may use such compounds as a 25 (potential) salt groups are located as near as possible to aminopyridine and N,N-dimethylhydrazine; the ends of the chains so that a very distinct block struc (2) Inorganic bases, compounds which are basic in re ture is formed as far as possible, with a hydrophobic chain action or which split off bases, such as ammonia, mono segment of 130-400 chain members being present. This is valent metal hydroxides, carbonates and oxides, such as achieved, for example, by first preparing a higher mo sodium hydroxide and potassium hydroxide. One may also 30 lecular weight prepolymer from polyhydroxyl compounds use a combination of different salt forming compounds. and polyisoyanates which are free from (potential) salt The carboxyl groups of such compounds may be only groups and then reacting this prepolymer with chain partly neutralized. lengthing agents which carry (potential) salt groups, more Cationic and anionic polyurethane polyelectrolytes can polyisocyanate and the component which carries at least also be prepared by subsequently modifying nonionic 35 one acylated amino group or the component which carries polyurethanes to render them cationic or anionic by addi at least one and preferably more than one methylol group. tion reactions. Thus, for example, polyurethanes which According to a preferred procedure, the polyurethane have unsaturated C=C double bonds may be modified electrolytes which are to be dispersed should have a mo to form polyelectrolytes by the addition of compounds lecular weight of less than 25,000, preferably 2,000 to which contain at least one OH, SH, NHR or SCl group 40 10,000 and have terminal groups of the general for which is capable of addition reactions, and another group mula - X-NHR which are reactive with formaldehyde, which is capable of salt formation, e.g. R OH -NR-CO, -NR-CS-, -O-CO-, -S-CO, -N1 (R-H or alkyl), -i. -, -COOH, -SO3H or -K -O-CS-, -OSO-, -CNR, -NR-CNR, YR R 45 -CO-NR-CO-, -CS-NR-CS or a corresponding salt group. The following are examples of such compounds which are capable of undergoing addition reactions: Thioglycollic acid, glycollic acid, 6-chlorosulphenylpro pionic acid, (3-alanine-Na, lysine, dimethylaminoethanol, 50 diethylaminoethylmercaptan, N,N-dimethylpropylenedi amine, methyl-2-hydroxyethylsulphide, ethyl-2-mercapto ethylsulphide, taurine, N-methyltaurine, 2-mercaptoethyl l, sulphonic acid sodium, N,N-dimethylhydrazine, N,N-di methylethylenediamine and sodium hydrogen sulphite. 55 Polyurethanes which are themselves nonionic may also be ionically modified by reaction with monoisocyanates and Z represents which contain tertiary amino, sulphide or reactive halo gen groups. After conversion of the said groups into the salt form by reaction with tertiary amines or quaternizing 60 -NHR, -( ) or R agents or acids, the polyurethane is modified by ionic side chains. and R represents hydrogen (preferably) or an alkyl or The following are examples of compounds which are alkenyl radical with 1 to 4 carbon atoms, which may be suitable for carrying out such modifications: chloroethyl Substituted by OH,-OCH-,-OCH5, -CCl3 isocyanate, bromoethyl isocyanate, chlorohexyl isocya 65 -COOH nate, the isomers of chloromethylphenyl isocyanate, chlo romethyltolyl isocyanate, dimethylaminoethyl isocyanate, or -SO3H; R may also represent CN, COR', SOR' in adducts of amino alcohols, diamines and thioether alco which R' represents an alkyl, alkenyl, alkoxy or car hols or thioether amines with mono- and polyisocyanates, boxyalkyl radical with 1 to 4 carbon atoms. 70 These are, therefore, acylated amino end groups or and methyl mercaptoethyl isocyanate. quasi acylated amino groups which are situated on a Polyurethanes may even be ionically modified by reac polarized C=N double bond. Furthermore, R may also be tion with cyclic compounds which have 3-7 ring members part of a 5-7 membered heterocyclic ring containing 1 to which have salt type groups or groups which are capable 3 heteroatoms, e.g. O, S or N. The group-X-NH-R of salt formation after ring opening, e.g. dicarboxylic acid 75 may be situated inside or outside the ring. 3,756,992 15 - - - 16 The simplest way of preparing the polyurethane poly If strongly cross-linked products are desired as end electrolytes according to the invention is first to synthesize products after removal of water from the dispersion, e.g. a polyurethane which has terminal NCO groups and an by evaporation on a substrate, one may use the com average molecular weight of less than 20,000 (preferably pounds Y-X-NHR or Y-R-(X-NHR) in their bi 1,000 to 10,000) from the compounds with reactive hy functional or polyfunctional form during the synthesis of drogen atoms mentioned earlier and a molar excess of the NCO-containing prepolymer. polyisocyanates. This corresponds to a free NCO group Compounds of the formula Y-X-NHR include, for content of 0.3-20 percent (preferably 0.8-10 percent). An example, the following classes of compounds: ureas, NCO group content of between 1.5 percent and 6 percent sulphamides, semicarbazides, guanidines, oxamides, biu is particularly preferred. The quantity of NCO groups O rets, sulphonyl ureas, hydrazodicarbonamides, urethanes, present is then generally at least 2 per polyurethane mole cyanamides, acid amides, cyanuric acid amides, imida cule. Such prepolymers are obtained in known manner by Zolidones, tetrahydropyrimidones, hexahydropyrimidones, using an NCO/OH ratio of between 1.1 and 2. urones, hexahydro-1,3,5-triazinones and the correspond According to a special embodiment of the process, this ing thio compounds. prepolymer is then reacted with compounds which con Individual representatives of these classes of compounds tain at least one of the groups X-NH-R defined above which are suitable for use in the process according to the and in addition a group Y which can react with NCO invention, are, for example, urea, thiourea, sulphamide, groups. This group Y may, for example, be -OH, -NH2, semicarbazide, thiosemicarbazide, N-hydroxyurea, guani -NH-R1, -SH, -COOH, -CONH2, -CSNH2, dine and its Salts, methyl urea, ethyl urea, butyl urea, -CO-NH-NH2, -NH-CO-NH2 20 methyl thiourea, allyl thiourea, methyl sulphamide, meth yl semicarbazide, methyl thiosemicarbazide, methyl -NH-CS-NH2 guanidine, oxamide, thiooxamide, biuret, thiobiuret, imino or -NH-NH2. oxamide, dithiooxamide, dithiobiuret, iminothiooxamide, The compounds which are suitable for reaction with the aminosulphonyl urea, hydrazodicarbonamide, thiohy prepolymers which contain NCO groups are thus at least 25 drazodicarbonamide, guanyl urea, aminosulphonyl thio monofunctional both towards isocyanates and towards urea, dithiohydrazodicarbonamide, guanyl thiourea, gua formaldehyde and have the general formula Y-X-NHR nidinothiourea; N-aminooxamide, N-aminothiooxamide, or Y-R-(X-NHR) wherein X and Y have the mean hydrazocarboxylic acid ureide, hydrazocarboxylic acid ings indicated above, R is a monovalent or higher valent thioureide, iminooxamide hydrazide, guanidino carbohy organic radical, and n is 1-4. R is preferably an aliphatic, 30 drazide, N-aminosulphamide, aminoguanidine, methyl aromatic, cycloaliphatic or araliphatic radical with 1-18 amino guanidine, guanidinourea, N,N'-dimethyl urea, N, carbon atoms which may also be substituted by alkoxy N'-diethyl urea, ethylene urea (imidazolidone), 4,5-dihy groups or halogen atoms. It is evident that -X-NHR droxyimidazolidone, 4,5-di-methoxyimidazolidone, hexa may be the same as Y, since, for example, the carbon hydropyrimidone, melamine, 5 - methyl-1,3,5-hexahydro amide or the urea radical may react both with isocyanates 35 triazone, 5-ethyl-1,3,5-hexahydrotriazone, 1 - oxa-3,5-di and with formaldehyde. azinone, 4 - ureido-6-methyl - hexahydropyrimidone, 4 The compounds Y-X-NH-R and ureido - 5 - hydroxyethyl-6-methyl-hexahydropyrimidone and other condensation products of urea with formalde hyde, acetaldehyde or isobutyraldehyde, triacetone diurea, include, apart from these specific compounds which are 40 tetrahydropyrimidone, 4,6,6 - trimethyl-2-thionotetrahy directly formulated according to the definition of X and dropyrimidone, methyl allophanate, trimethyl biuret, Y, so-called aminoplast-forming NH-containing compo phenyl biuret, benzoyl biuret, amino biuret, cyanogen nents as defined for example in Angewandte Chemie 76, urea; biguanide, ammeline; thioammeline, carbonyl di 909-919 (1964) and described therein (see also A. Bach urethane, urea dicarboxylic acid diamide, trimethylol mann and Th. Bertz.: Aminoplaste, 1967, VEB Deutscher 45 melamine, guanazole, guanazine, dicyandiamide, 1 - hy Verlag fir Grundstofindustrie). droxy-2,2,2-trichloroethyl urea, N,N'-bis(1-hydroxy-2,2,2- The essential condition is that the preformed poly trichloroethyl urea, acetylurea, trichloroacetyl urea, ben urethanes which carry 0.3 to 20 percent of free NCO Zoyl urea, triuret, hexahydropyrimidone, acetyl guanidine, groups should react with the compounds Y-X-NHR or trichloroacetyl guanidine, methylsulphonyl urea, ethyl Y-R-(X-NHR) and not with chain lengthening to 50 sulphonyl urea, phenyl urea, N,N'-diphenyl urea, N,N'- form high molecular weight polyurethanes. In practice ditolyl urea, N,N-o-phenylene urea, perinaphthylene urea, chain breaking should occur so that the average molecular ethylene urea, acetylene urea, dimethylacetylene diureine, weight does not exceed 25,000 and is preferably between diphenylacetylene diureine, 2,4-dimethylsemicarbazide, o 2,000 and 10,000. The average molecular weight can be hydroxy-ethylisourea, diphenylguanidine, N - methyl-N'- estimated sufficiently accurately by, for example, end 55 acetyl-guanidine, amino guanidine, anilidoguanidine, N group determination of viscosimetric and osmometric amino - N - phenyl - guanidine, acetoguanamine, aceto molecular weight determination. guanide, oxamidic acid, oxalauric acid, thio-oxamidic acid, The most important factor when carrying out the reac methylol urea, N,N'-bis-methylol urea, hydroxyethyl urea, tion, in practice, is that when the formaldehyde-contain N,N'-bis-hydroxyethyl urea. ing solutions are subsequently added, one should be able 60 Compounds of the formula Y-R-(X-NH-R) in to mix the substance, e.g. as a solvent free melt, with them clude the following: glycollic acid amide, glycollic acid thoroughly by means of the usual mixing apparatus. The thioamide, hydroxymethylsulphonamide, hydroxymethyl resulting polyurethane mass which contains terminal urea, hydroxymethyl thiourea, iminoglycollic acid amide, X-NHR groups should therefore have a viscosity of less hydroxymethyl guanidine, glycine amide, glycine thio than 1,500 poises at 120° C. The viscosity is preferably amide, aminomethyl sulphonamide, aminomethyl urea, 50-1,000 poises. aminomethyl thiourea, iminoglycine amide, aminomethyl Although the compounds Y-X-NHR or guanidine, sarcosine amide, sarcosine thioamide, butyl aminomethyl sulphonamide, thioglycollic acid amide, thio glycollic acid thioamide, malonic acid diamine, thiomalo with which the prepolymers are mainly modified accord nic acid diamide aminosulphonyl acetamide, ureidoacet ing to the invention are predominantly monofunctional in amide, thioureidoacetamide, carbamic acid-glycollic acid their reaction with isocyanates, they may also be partly amide ester, carbamic acid-thioglycollic acid amide ester, incorporated as bifunctional compounds into the poly thiocarbamic acid-glycollic acid amide ester, amidosul urethane moleculae, provided that the molecular weight phonic acid glycollic acid amide ester, guanyl acetamide, or viscosity thereof, do not rise above the given limits. 75 guanidino acetamide, malonic acid dithioamide, amino 3,756,992 17 8 Sulphonyl thioacetamide, ureidothioacetamide, thioureido and hydroxyphthalic acid diamides, citric acid diureides, thioacetamide, carbamic acid glycolic acid thioamide amino-phthalic acid diureide, aspartic acid diureide, car ester, ureidomethylsulphonamide, methylene - bis - urea, bamic acid-2-hydroxyethyl ester, hydroxymethyl dicyandi ureidomethyl-thiourea, ureidomethylguanidine, thioureido amide, N,N'-hydroxyethyldicyandiamide, 6-methylamino methylsulphonamide, methylene-bis-thiourea, thioureido caproic acid amide, 6-aminocaproic acid amide, 6-amino methyl guanidine, malonic acid amide hydrazide, amino caproic acid methylamide, 6-methylaminocaproic acid sulphonyl acetohydrazide, ureidoacetohydrazide, thiourei methylamide, 6-aminocaproic acid ethanolamide, maleic doacetohydrazide, carbamoylacetohydrazide, amidosul acid bis-amide, phthalic acid bis-amide, isophthalic acid phonic acid glycollic acid hydrazide, guanidonoacetohy bis-amide, terephthalic acid bis-amide, hydroxyethoxy drazide, glycollic acid ureide, glycine ureide, sarcosine 0. propionic acid amide, hydroxyhexyloxypropionic acid ureide, thioglycollic acid ureide, malonic acid amide amide, 6-aminocaproic acid ureide, 11-aminoundecanoic ureide, malonic acid thioamide ureide, ureidoacetoureide, acid ureide, p-aminobenzamide, p-aminobenzureide, and malonic acid ureidohydrazide, hydrazino-acetoureide, hy glutaric acid amide. drazinoacetamide, hydrazinothioacetamide, aminosul The above-mentioned compounds Y-X-NHR or phonyl methylhydrazine, hydrazinomethyl urea, hydra 5 Y-Ra-(X-NHR) may either be used in quantities Zinomethyl thiourea, carbamoyl methyl hydrazine, glycol equivalent to the NCO groups present or in excess. A ratio lic acid thioureide, glycine thioureide, ethylaminometh of 1.0:1 to 2.5:1 and in particular 1.0:1 to 1.5:1 is y1 urea, N-methyl-N'-methylaminomethyl urea, malonic preferred. acid monoamide, carboxymethyl urea, carbamylacetic It may sometimes be desired, especially in view of a acid, thiocarbamyl-O-acetic acid, thiocarbamyl-S-acetic 20 branched and, therefore, subsequently cross-linked molec acid, amidosulphonic acid-glycollic acid ester, carboxy ular structure, to carry out the process below the equiva methyl guanidine, guanyl acetic acid, malonic acid mono lence and preferably in the equivalent ratio 0.6-1. In this ureide, 2-hydroxypropionic acid amide, 1-hydroxypro procedure the NCO/OH-ratio may be higher than 2 and pionic acid amide, 2-hydroxyethylthiopropionamide, 2-hy up to 3 when building up the prepolymer. droxyethyl sulphonamide, N - methyl-2-hydroxyethylsul 25 End groups of the formula -X-NHR are also formed phonamide, 2-hydroxyethyl urea, 4,4'-diureidomethyldi by reacting prepolymers which have terminal NCO groups phenyl oxide, ethylene-bis-methanesulphonamide, hexa with ammonia or primary amines, for example with methylene-bis-p-toluene sulphonamide, 4,4'-diureidometh methylamine, ethylamine or ethanolamine. For this pur ylbenzene, N,N'-bis-(2-hydroxyethyl)-urea, N,N,N'-tris pose, it is advantageous to introduce the amine com (2-hydroxyethylurea), N,N-bis(2-hydroxyethyl)urea, 2 30 ponent into the reaction vessel and then add the prepoly hydroxyethyl thiourea, N,N-bis-(2-hydroxyethyl)-thio mer. Alternatively the amine may be converted into the urea, 2 - hydroxyethylurethane, ethylene-glycol-bis-car carbonate to reduce the reactivity. The reaction may bamic acid ester, 2-hydroxyethylguanidine, 2 - hydroxy be carried out in the presence of water. propionic acid ureide, 6-alanine amide, ox-alanine amide; Urea, thiourea, alkylene-bis-ureas, aminocarboxylic sarcosineamide, taurine amide, N-methyl-taurine amide, 35 acid amides and ureides, imidazolidone and amino deriva 2-amino-ethyl urea, 2-aminoethyl thiourea, 2-aminoethyl tives of triazine are particularly preferred for this pur urethane, S-(2-hydroxyethyl)-thiourethane, O-(2-hydroxy pose. ethyl)-thiourethane, 2-hydroxyethyl sulphuric acid amide, R is preferably a hydrogen atom, i.e. the compounds guanyl ethanol, guanyl ethylamine, 2 - aminoethylguani in question are preferably acyl derivatives of ammonia. dine, 2-mercaptopropionic acid amide, 2-mercaptoethyl 40 Such end groups -X-NH2 insure especially high re sulphonamide, succinic acid monoamide, maleic acid activity with formaldehyde and reactive methylol com monoamide, 2-carboxyethyl sulphonamide, 2-carboxy pounds and their ethers, a factor which is especially im ethylurea, 2 - carboxyethyl urethane, 2-guanyl propionic portant when preparing dispersions which undergo spon acid, 2-carboxyethyl guanidine, succinic acid monoureide, taneous cross-linking at room temperature or only slight succinic acid diureide, fumaric acid diureide, malonic acid ly elevated temperature. Among the substituted ureas, diureide, succinic acid diamide, amidosulphonyl propionic 45 imidazolidone (ethylene urea) and its derivatives are par acid amide, 2-carbonamidoethyl urea, 2-carbonamidoethyl ticularly reactive and therefore preferred. urethane, 2-carbonamidoethyl sulphuric acid amide, 2 Some of the compounds listed as anionic modification guanyl propionamide, 2-carbonamidoethyl guanidine, suc components are also suitable for use in the reaction cinic acid amide ureide, succinic acid dithioamide, suc with prepolymers which contain NCO groups, leading cinic acid amidohydrazide, hydrazinocarbonylethyl urea, 50 to formation of polyurethanes which carry end groups hydrazinocarbonylethyl urethane, amidosulphonylethyl which are reactive with formaldehyde. These are usually urea, ethylene-bis-urea, carbamylethyl urea, guanylethyl compounds which contain at one and the same time a urea, guanidinoethyl urea, ureidopropionic acid ureide, group which is reactive with NCO groups, and amide ethylene-bis-thiourea, 2 - hydrazinopropionamide, 2 - hy or ureide group and a carboxylic or sulphonic acid group, drazinoethyl urea, 2-hydrazinoethyl thiourea, 2-dihydra if desired in salt form. Zinoethyl urethane, guanyl-ethyl hydrazine, 2-hydrazino The following are examples of these compounds: dihy ethyl guanidine, 2-hydrazinopropionic acid ureide, 3-hy droxymaleic acid monoamide, tartaric acid monoureide, droxybutyramide, 3-hydroxypropyl urea, N,N'-bis-(3-hy citric acid mono and diamide; citric acid mono- and droxypropyl)urea, N,N-bis-(3-hydroxypropyl)urea, N,N- diureides, tartaric acid amide, asparagine, glutamine, bis-(3-hydroxypropyl)thiourea, 3-hydroxy-propylurethane, 60 aspartic acid monoureide, glutamic acid monoureide, 3-hydroxypropylguanidine, leucine amide, isoleucine, ureidosuccinic acid, oxaluric acid, acetamide-C-Sulphonic amide, 3-aminopropyl sulphonamide, 3-aminopropyl urea, acid, acetyl urea-C-sulphonic acid, acetylguanidine-C-sul 3-aminopropyl thiourea, 3-aminopropyl urethane, guanyl phonic acid, propionyl urea o-Sulphonic acid, propion propylamine, 3-aminopropyl guanidine, 3-carboxypropyl amide ox-sulphonic acid, butyramide a-sulphonic acid, iso urea, glutaric acid diamide, 3-carbonamidopropyl urea, 3 65 butyramide cy-sulphonic acid, acetoguanamine sulphonic guanyl-butyramide, 3-carbonamidopropyl guanidine, tri acid, N-methyl-asparagine, N-methyl-aspartic acid ureide, methylene - bis-urea, trimethylene-bis-thiourea, 3 - hy N-hydroxyethyl-asparagine, N-hydroxyethyl aspartic acid drazinobutyramide, 3 - hydrazinopropylurea, 4-amino ureide, addition products of aminoamides or aminoureides butyric acid amide, 5 - aminovaleric acid amide, 6 70 with a,6-unsaturated carboxylic acids, of aminocarboxylic amino-caproic acid amide, 11 - aminoundecanoic or aminosulphonic acids with o,3-unsaturated carboxylic acid amide, 1,4 - tetramethylene-bis-urea, 1,6 - hexa acid amides or -ureides, N-carbonamido methyl glycine, methylene-bis-urea, 2.2 - dimethyl - 1,3 - trimethylene N-carbonamidomethyl-6-aminohexanoic acid, N-carbon bis-urea, malic acid diamide, aspartic acid diamide, citric amidomethyl anthranilic acid, carboxylmethyl-amino acid diamide, the isomeric aminophthalic acid diamides 75 acetyl urea, addition products of sultones and 6-lactones 3,756,992 19 20 such as 6-propiolactone with ureas and carbonamides such glycols in the polyurethane, may also be used as a method as 3-ureidopropane sulphonic acid, 3-ureidobutane Sul for introducing terminal acylated amino groups. phonic acid and 2-ureidopropionic acid. The total quantity of acylated amino groups It is as well possible to use addition products which are formed by an aminomethylation or sulfomethylation reaction to ureas or carbonamides. It is advantageous that may be greater than that of the end groups themselves the addition of sultones, lactones and carboxylic acid because such groups can also be introduced by means of anhydrides as well as the aminomethylation and sulfo bifunctional chain lengthening agents, alkylating agents methylation can also be effected, before the dispersion or neutralizing agents (acids or bases). The total quantity process, on the polyurethane containing acylated amino O should, however, not exceed 400 millieduivalents percent end groups. and is preferably 20-120 millieduivalents percent. Analogously, the corresponding (potential) cationic By the term "terminal group' is meant a group which compounds, e.g. c. - dimethylamino-6-hydroxypropion depending on the specific -X-NH-R used is linked amide, may also be used. only at one part to a relatively long radical, while R The end groups -X-NHR or -X-NH2 can, of should not contain more than 4 carbon atoms. course, also be introduced in the polyurethanes in some other manner, for example by using poly(ester) amides which carry carbonamide or ureide groups entirely or can therefore also be a side branch of such a main chain partly in terminal positions, using in this case, less than or the end group of such a side branch. A polyurethane the equivalent quantity of diisocyanate. 20 molecule should, on an average, contain about 1.5 to In another method, polyesters with terminal carboxyl 10 such terminal groups but preferably 2 to 5 such ter groups or low molecular weight polycarboxylic acids are minal groups. used as structural components. After reaction with less The introduction into the polyurethane of terminal than equivalent quantities of polyisocyanate, a polyure groups which are reactive with formaldehyde is carried thane with terminal carboxyl groups is obtained; these 25 out at temperatures between room temperature and about carboxyl groups are reacted with ammonia and heated so 190° C. Temperatures between 80 and 160° C. are pre that they (partly) form acid amide groups in known ferred. At higher reaction temperatures, there is the risk late of incipient decomposition of the polyurethane polyelec In yet another method polyurethanes which have termi trolytes, whereas at lower temperatures stirring becomes nal tertiary amino groups are quaternized with an alkylat 30 more difficult. The selected reaction temperature also de ing agent which contains an acylated amino group pends on the reactivity of the compounds which is added X-NHR. Polyurethanes with terminal sulphide groups to the prepolymer to provide the end groups. can also be terminated in a corresponding manner with The reaction of a prepolymer which has free -NCO alkylating agents. The preparation of polyurethanes with groups with, for example, 6-aminocaproic acid amide takes terminal tertiary amino groups has been described, for 35 place sufficiently rapidly at 80° C. and below, whereas example, in Belgian patent specification No. 636,799. To the reaction with urea requires temperatures above 120 prepare such polyurethanes which have terminal tertiary C. In general, it is advantageous to operate at tempera amino groups, it is advantageous to react the correspond tures above the melting point of the added component ing NCO prepolymers with, for example, dimethyl amino if solubility is insufficient. ethanol, dimethyl aminopropanol, N,N-dimethylhydra 40 According to another embodiment of the process, pre zine, N,N - dimethylethylene diamine, N,N-dimethyl polymers which carry free NCO groups and which con aminopropylamine or N,N-dimethylaminohexylamine. tain 0.3–20 percent and preferably 0.8-10 percent of Suitable alkylating agents are, for example, chloroacet NCO are reacted with compounds which have at least amide, bronoacetamide, N - methylchloroacetamide, 6 one but preferably at least two free reactive methylol bromopropionic acid amide, ox-chloropropionic acid groups. Prepolymers which contain 1.5-6 percent of free amide, ox-bromopropionic acid amide, ox-bromoisobutyric 45 NCO are particularly preferred. acid amide, m-chloromethylbenzamide, p-chloromethyl These compounds which carry free methylol groups benzamide, p-chloromethylbenzamide, 4 - chloromethyl are, for example, the mono-, di- and oligomethylol com phthalic acid diamide, c-bromosuccinic acid diamide, 2 pounds of the compounds Y-X-NHR or chloro - 4,6-diamino-s-triazine, 2 - chloro - 4 - methoxy 6 - amino-s-triazine, ox-methylsulphonyl-hydroxy-succinic 50 acid diamide, ethylsulphonyl hydroxyacetamide and which have been defined above, methylol compounds of chloroacetyl urea. aliphatic and araliphatic ketones; nitriles or B-ketocarbox Polyurethanes which have terminal reactive halogen ylic acid esters and quite generally of compounds which atoms, the preparation of which has been described, for have CH acidic hydrogen atoms, as well as of phenols, di example, in Belgian patent specification No. 636,799, can 55 and polycarboxylic acid amides and di- and oligoure be quaternized similarly with tertiary aminoamides, e.g. thanes. The one restriction on the compounds used for with dimethylaminoacetamide, 2 - diethylaminopropion this purpose is that, to be for the reaction with NCO pre amide, dimethylamino succinic acid diamide, p-diethyl polymers, they must have at least one free methylol group aminomethyl benzamide, m-dimethyl-aminobenzamide, 2 left after the reaction with the isocyanate groups present. dimethylaminopropionic acid amide or 2-dibutylamino 60 The following are examples of suitable methylol com propionic acid amide. pounds: dimethylol urea, tetramethylol urea, trimethylol In yet another method, polyurethanes which have been melamine, tetramethylol melamine, pentamethylolmel prepared in known manner, for example with terminal amine, hexamethylolmelamine, tetramethylol hydrazodi -OH, -SH, -NH2 groups, can be converted into poly carbonamide, dimethylol dicyandiamide, pentamethylol 65 4-ureido - 6 - methyl-hexahydropyrimidone, dimethylol-p- urethanes with terminal amide groups by addition of CreSol, tetramethylolacetone, hexamethylol acetone, tetra acrylamide or acrylonitrile followed by partial hydrolysis. methylol methylethylketone, pentamethylol methylethyl The electrolyte-forming group is introduced at the same ketone, tetramethylol hexanone and dimethylolithiourea. time by addition of, for example, maleamic acid or In addition, methylol compounds of the compounds al maleuric acid. 70 ready mentioned which carry end groups which are re The addition of, for example, hydroxylamides, hydroxy active with formaldehyde may be used. alkyl ureas, mercaptoalkylamides, aminoalkylamides, or Methylol-containing condensation products of urea aminoalkylthioureas to terminal double bonds which are formaldehyde, urea acetaldehyde-formaldehyde, urea fur capable of addition reactions, such as those obtained by furolformaldehyde, urea crotonaldehyde - formaldehyde the incorporation of unsaturated dicarboxylic acids or 75 and melamine formaldehyde may also be used. In gen 3,756,992 2. 22 eral, many different methylol-containing phenol formal sufficient for subsequent chain lengthening. If one intends dehyde or amine formaldehyde condensation products to carry out dispersion in the presence of formaldehyde, such as those commonly described as phenol resins or the amount may be still less. amine resins and which are produced commercially may The reaction of the starting components to convert be used. Xylene-formaldehyde resins which contain meth them into (potential) polyurethane electrolytes, in par ylol groups may also be used. 5 ticular the last stage, of the process (reaction of the NCO Low molecular weight polymers and copolymers based prepolymer with compounds Y-X-NH-R or on acrylamide or methacrylamide and formaldehyde may also be used. Any of the methylol compounds of di- and oligoure O or their methylol compounds) can also be promoted by thanes, such as those formed generally from polyisocya the addition of small quantities of solvents such as di nates and alcohols, from polyisocyanates and polyalcohols methyl formamide, diethyl formamide, ethylene glycol, or from monoisocyanates and polyalcohols, may be used. diethylene glycol and their ethers and esters. The quantity Examples of these are methylol compounds of the ad of solvent thereby introduced should be not more than ducts of: 1,6-hexane diisocyanate and methanol, ethanol about 6 percent of the total amount of polyurethane dis or propanol; 2,4-toluylene-diisocyanate, trimethylol pro persion. The quantity is, however, preferably only 0.2-2 pane, and methanol; triphenylmethane triisocyanate and percent. The use of solvents which have hydroxyl groups methanol; pentaerythritol and methylisocyanate; and tri which are later built into the polyurethane under the ac methylol propane and methoxymethyl isocyanate. tion of the formaldehyde added is especially advantageous. The methylol-containing substance which is used is gen In the quaternization reaction of a potential polyure erally nonionic and neutral in its electronic character. It thane electrolyte which contains basic nitrogen atoms with is then reacted with an NCO prepolymer which itself has chloroacetamide, sublimation of the amine on the cool a (potentially) electrolytic character, for example by parts of the reaction vessel may be prevented by the addi virtue of built-in cationic or anionic salt groups or the initial presence of basic amino groups, sulphide groups or tion of, for example, 1-3 percent ethylene glycolmono carboxyl groups. 2 35 methylether acetate. One may, however, also start with prepolymers which It should be emphasized, however, that the process are free from ionic groups or potential ionic groups and according to the invention is preferably carried out with react these prepolymers with methylol compounds which out organic solvent. The special advantage of the process carry (potentially) ionic groups; in particular with those according to the invention compared with prior art proc which carry basic amino, quaternary ammonium, carboxyl 30 esses is that the use of an organic solvent to obtain poly or sulphonic acid groups or their salts. urethanes from aqueous dispersion can be completely dis The following are examples of such compounds: meth pensed with without any disadvantages being incurred. In ylol compounds of dihydroxymaleic acid monoamide, addition the dispersions formed do not have to be subjected tartaric acid monoureide, citric acid mono- and diamide, to a distillation process and do not require any special citric acid mono- and diureide, tartaric acid amide, precautions on account of the presence of residual quanti asparagine, glutamine, ureidosuccinic acid, succinic acid ties of solvent. One may, of course, use water as solvent monoureide, maleamic acid, maleuric acid, acetyl urea C even at this stage of the reaction. sulphonic acid, N-hydroxyethyl asparagine, N-hydroxy The absence of organic solvents in the process accord ethyl aspartic acid ureide, N-carbonamidomethyl glycine, ing to the invention is possible because in contrast to the sodium sulphomethyldicyandiamide, and methylol-con 40 prior art processes, low molecular weight polyurethanes taining aminoplast and phenolplast precondensates which which are free from NCO groups are dispersed by mixing have an electrolyte character due to the inclusion of With Water. A chain lengthening reaction occurs only (potentially) ionic components. These ionic components during, or some time after, dispersion, being brought are generally used together with the usual components about by heat treatment and if desired by lowering of such as urea, melamine, cyanamide, dicyandiamide, phe 45 the pH. This reaction may lead either to the formation nol, cresol, aldehydes, and ketones are, for example, gly of a thermoplastic resin or to the formation of a high cine, taurine, N,N-dimethylethylene diamine and chloro molecular weight resin which may be cross-linked to a acetamide. greater or less extent. This chain lengthening reaction The methylol compounds may be used in quantities to form the high molecular weight polymer takes place equivalent to the NCO groups present, i.e. one mol of 50 without substantial increase of viscosity in the aqueous methylol compounds to one NCO equivalent, but they binary system and/or only later, during shaping. also may be used in excess. Preferably, an equivalent ratio When synthesizing potentially cationic polyurethanes of 1.0 to 2.5 and especially 1.0 to 1.5 is used. with built-in tertiary amino groups, one can usually dis Methylol end groups can, of course, also be introduced pense with compounds which catalyze the reaction with in some other way, for example, by reacting polyurethanes isocyanates. The use of a catalyst may be advantageous which have terminal double bonds, epoxides, carboxyl or when synthesizing sulphonium polyurethanes or polyure anhydride groups with the methylol compounds. thanes which carry anionic groups. Tertiary amines and In another method, reacting polyurethanes which have organometallic compounds, e.g. tributylamine, diazabi reactive halogen atoms which are capable of quarteniza cyclooctane, pyridine, tin octoate, dibutyl tin dilaurate, tion are reacted with methylol compounds which contain 60 Zinc octoate, cobalt naphthenate and iron acetyl acetonate tertiary amino groups. Conversely, polyurethanes which are especially advantageous for such a purpose. contain terminal amino groups, such as those described, Polyurethane polyelectrolytes which contain groups that for example, in Belgian patent specification No. 636,799 are reactive with formaldehyde and which according to can also be reacted with quaternization with methylol the invention are converted with formaldehyde-containing compounds which carry reactive halogen atoms. 65 Solutions into methylol-containing polyurethane polyelec Suitable compounds with reactive halogen atoms, in trolytes during or immediately before dispersion should clude the methylol compounds of the haloalkyl acid have an average molecular weight of less than 25,000 amides mentioned earlier. Suitable compounds with ter and preferably between 2,000 and 10,000. tiary amine groups are, for example, the methylol com Polyurethane polyelectrolytes having molecular weights pounds of the aminoamides mentioned earlier. O between 3,000 and 8,000 are especially preferred. In ad The polyurethane electrolytes may, of course, only con dition, they should no longer contain any free NCO tain a certain proportion of methylol groups in addition groups. The average molecular weight is difficult to deter to acylated amino groups -X-NHR which are reactive mine exactly but can be estimated with sufficient accuracy, with formaldehyde. Thus an amount of, on an average, for example, by group determination and osmometric about one reactive methylol group per molecule is often measurements. In many cases the approximate average 3,756,992 23 24 molecular weight can be determined from the stoichem Since salt formation in an anhydrous medium is usually istry of the reactants employed for the synthesis of the associated with a high increase in viscosity, it may be ad polyurethane. vantageous, especially in the case of those polyurethanes If, for example, 2 mols of a dihydroxy compound of which are in any case highly viscous, to carry out salt for molecular weight 2,000, 1 mol of a basic chain lengthen mation with acids or bases only during the addition of ing agent of molecular weight 119, 4.75 mols of diisocyan Water. ate (molecular weight 168) and 3.5 mols of urea (molecu Salt groups and groups capable of salt formation may, lar weight 60) are reacted together to produce a polyure of course, also be present at the same time. thane with 2 terminal biuret groups, then the molecular In order to achieve satisfactory dispersion as well as weight is calculated to be: O satisfactory properties in the end products, it is also necessary that the (potential) polyurethane electrolytes 3MW-2/3.5. (2X2,000-119 should have hydrophobic chain segments of at least 60 -4.75x168-3.5x60)a-3000 chain members. By “hydrophobic chain segments' are This calculated molecular weight is almost invariably meant segments which contain neither salt groups nor below 10,000 and is usually below 8,000. groups capable of salt formation which are converted into Another important factor in practice is that the vis salt groups in the course of the process. These hydro cosity at 120 C. should be less than 1500 poises. The vis phobic segments are advantageously polyether, polyester, cosity is preferably between 50 and 1,000 poises. At polythioether or polyacetal segments which may also be higher viscosities, admixture of aqueous formaldehyde interrupted by longer hydrocarbon radicals or urethane containing solutions is difficult and requires the use of 20 or urea groups. Those polyurethanes in which these hydro Special apparatus such as internal mixers, mixing screws phobic segments consist of 250-400 chain members and or slowly rotating spiral stirrers. In addition there is the only contain small number (e.g. 4-10) urethane or urea risk of premature increase in molecular size in the stages groups, are particularly preferred. up to chain lengthening, before the process of dispersion According to a preferred embodiment of the process, is completed. If no suitable measuring apparatus is avail water together with formaldehyde and if desired together able, one can take as a general guide the fact that the with acids or, bases for neutralization, potential Salt reaction mass should be sufficiently stirrable in a 3 liter groups are stirred at elevated temperatures into the glass beaker at 120° C. using an ordinary horseshoe mixer (potential) polyurethane electrolyte which have terminal at 50-200 revS./min. reactive acylated amino groups. Products which have viscosities below 50 and espe 30 According to a further preferred embodiment of the cially those with viscosities below 10 are of little practical process, water is first added to the polyurethane mass until interest because the properties of the end products render it appears cloudy. This quantity of water may contain the them of little use. quantities of bases or acids required for neutralization of It should be noted that in the polyurethane polyelec acid or basic groups. This first quantity of water amounts trolytes used according to the invention which contain 35 to about one tenth to one quarter of the weight of the end groups which are reactive with formaldehyde, there polyurethane mass. The temperature is preferably between is no fixed relationship between viscosity and molecular 50 and 100° C. Aqueous formaldehyde is then added Weight. However, for a given definite chemical composi within the same temperature range, followed by Water. tion the viscosity increases with the molecular weight. During the addition of water, the temperature may be The viscosity is much more influenced by the chemical 40 150° C. If desired, this operation may be carried out under character of the polyurethane and in particular the preSSure. amount and sequence of ionic groups and groups capa The necessary quantity of formaldehyde may also be ble of hydrogen bond formation. dissolved in the total amount of water required for dis The polyurethane electrolytes which contain terminal persion, and this formaldehyde solution may be added groups which are reactive with formaldehyde preferably gradually. have a salt group content of 4-120 milliequivalents per 45 Alternatively, a concentrated solution or suspension cent. This means that for an average molecular weight containing formaldehyde may first be added to the poly of 2,500 at least every tenth molecule incorporated car urethane melt (e.g. a suspension of paraformaldehyde in ries a salt group. These portions of the polyurethanes a little water), and the resulting polyurethane mass may which carry salt groups then act as emulsifiers for the non then be dispersed by admixture of water. Paraformalde ionic portions, Salt groups of various types of chemical 50 hyde or compounds which give off formaldehyde may constitution may be used. also be added in succession to the reaction mass, in which The following are the most commonly used groups: case an aqueous solution which contains formaldehyde is formed in situ. It is also possible to predisperse the polyurethane elec 55 trolytes having terminal reactive acylated amino groups with water and to add, in the last reaction step, formal dehyde in free or dissolved or chemically bonded form. This method of working is especially advantageous if, YR during the dispersion process, pH-values below 4 or above The same applies to polyurethane electrolytes which carry 60 9 must be applied and there is a danger of a premature methylol groups. polycondensation during the dispersion process. The polyurethanes need not already be present in the The only essential condition to be observed in this salt form before addition of the aqueous solution which embodiment of the invention is that at least some por contains formaldehyde. Instead, these groups may be tions of water added should contain formaldehyde. present in a potential form, i.e. as groups which are capa Instead of free formaldehyde, aqueous solutions of ble of salt formation. This is especially advantageous if substances which give off formaldehyde, especially solu salt formation takes place by simple neutralization in the tions of paraformaldehyde, trioxane, methylal, hexa presence of water. methylene tetramine, oligo-methylol compounds such The following are examples of groups which are capa 70 as di- and oligomethylol ureas, -hexahydropyrimidinones, ble of salt formation (potential electrolyte groups): -urones, -melamines and other triazine derivatives may be O used. Methylol ethers may also be used, provided that / -N-, -COOH, -SO3H, -P they are used together with acid catalysts and therefore FIN exist partly as free methylol compounds or free formal O R. 5 dehyde. 3,756,992 27 28 above 50° C. The length of time depends on the tempera agents. For this purpose, polyfunctional substances which ture and on the pH. At pH values of 5 to 7 and tempera have a cross-linking action and which cause chemical tures of about 50 to 80 C. the heat treatment does not cross-linking after the solvent, if present, has been evap need to last more than 10 to 48 hours. However, at orated at room temperature or elevated temperature, are 140 C. and a pH of 2, ten minutes may be sufficient. At added to the polyurethane masses in the course of the temperatures above 120° C., it is preferable to work in a process. Examples of these substances are sulphur, sulphur pressure vessel. sols, free and partially or completely masked polyiso According to a further preferred embodiment, the cyanates, carbodiimides, polyamides, primary mono resulting dispersion is stirred for 1 to 4 hours at a reac amines and ammonia and organic and inorganic per tion temperature of 90-110° C. immediately after it has O oxides. The cross-linking agents, fillers, pigments, blend been produced. The resulting after-reaction is strongly ing agents and other additives which may be present in accelerated by lowering the pH to 5 to 2 (preferably 4 to solutions or suspension may be added to the dispersed 3), for example by the addition of tartaric acid or phos polyurethane masses in the course of the process. Form phoric acid. aldehyde and/or higher aldehydes or their reactive This after treatment is necessary especially if the dis 5 derivatives and condensates, e.g. with amines and car persion is dried at room temperature and if after heating bonic acid derivatives, or di- and polyepoxides may be is not possible, for example in the cases of paints applied added afresh to the dispersion already formed. The acyl to buildings. ated amines Y-X-NHR or Y-R-(X-NH-R) In addition to or instead of this step, the dispersion may which have already been mentioned and which act as also be dried at an elevated temperature. Temperatures 20 cross-linking agents for the methylol compounds present below 100° C. are preferred for this purpose owing to the are of special importance as additive components. These risk of bubble formation. The dispersions are in most cases acylated amines may be added at any stage during the first adjusted to pH 5 to 2 (preferably 4 to 3) if one does Synthesis of the polyurethane mass or the dispersion not wish to carry out after heating at higher temperatures. thereof or even only shortly before application of the This method should be used, in particular, in the product 25 product. tion of continuous coatings, backings, bonds and lacquers Free polyisocyanates which have a molecular weight of where drying is carried out fairly rapidly in a drying between 110 and about 4,000, on the other hand, must channel. not be added until just before dispersion and preferably In addition to or instead of the these measures, the par. only after dispersion has occurred. They may also be tial or completely dried products may also be after heated, 30 added to the finished dispersion. e.g. after shaping. In Such a case, the finished coatings, Polyurethanes with different properties are obtained de lacquers etc. are heated to temperatures between 50 and pending upon the chemical composition of the product 200 C. (preferably 70-150° C.) and left at this tempera and the amount of urethane groups and ionic groups ature for some time. The drying temperature of the sur present. Thus soft, sticky masses, thermosplastic and rub roundings may be higher in the case of a quick drying bery elastic products with different degrees of hardness operation, but the temperature of the polyurethane should up to glassy duroplasts may be obtained. The hydrophilic not exceed 200 C. At this temperature, a drying time of character of the products may also vary within wide 30 seconds may be sufficient, although at 100° C., the after limits. The elastic products may also be worked up ther heating time may rise to 1 to 4 hours. The resulting aque moplastically for example, at 100 to 180° C., provided ous dispersions may be liquid or pasty in consistency and 40 they have not been produced with the addition of cross are stable without the addition of emulsifiers. However, linking agent. Small quantities of plasticizers or swelling suitable cationic, anionic or neutral emulsifiers and pro agents such as polyesters, polyethers, phthalates or phos tective colloids may be added, such as the casein which has phates or even water, are advantageously added for this been decomposed by acid or ammonia, soaps, invert soaps, purpose. alkyl sulphonates, polyvinyl alcohol, hydroxy-ethylated 45 Coagulates which are obtained, for example, by freez phenols, oley alcohol, polyglycol ethers, hydroxyethylated ing the dispersions or by the addition of electrolyte can polypropylene glycol or natural products such as gelatine, be converted into thin sheets, e.g. by pressing and drying, gum arabic; tragacanth or fish glue. Such additives serve and these sheets can then be further processed by the mainly to lower the relatively high surface tension of the usual methods. In some cases, aqueous dispersions may polyurethane dispersions. They also influence the chemical 50 also be atomized to form powders which can be sintered stability and the coagulability of the dispersions. The dis and melted. persions may be blended with dispersions of equal charge If the dispersions can sediment and be redispersed, the such as polyvinyl acetate, or dispersions of polyethylene, finely divided polyurethane may also be simply removed polystyrene, polybutadiene, polyvinyl chloride and copoly by filtration under Suction. The resulting pastes or pow mer resins. 55 ders can be solidified by melt sintering. Lastly, the prod Lastly, fillers, plasticizers, pigment, carbon black and lucts may be after treated with aqueous solutions of poly silicic acid and dispersions of aluminum, clay or asbes valent anions, e.g. of Sulphate disulphonate, phosphate, tos may be worked into the dispersions. silicofluoride or phosphate, to improve their properties, In many cases it is of advantage to incorporate the for example to increase the hydrophilic and lyophobic fillers, plastisizers, pigments, stabilizers e.g. against the 60 properties and their surface hardness. influence of light or hydrolyzing influences, cross-linking The polyurethanes obtainable by the process according agents, optical brighteners, agents effecting thixotropy, to the invention can be used in many different ways. agents for improving the surface properties and the hand Thus they can be used for producing dip molded of e.g. coatings in substance, in dissolved, suspended or articles and foams by the latex foam heating process. dispersed form, before the addition of water, into the They can be used to form coagulates by the addition of melt of the polyurethane or to the concentrated aqueous electrolyte to the aqueous solutions and dispersion, and solution of the polyurethane polyelectrolyte present these coagulates can be worked up on mixing rollers both before the dispersion process. sticky and nonsticky films and foils being obtained by The dispersions of the polyurethane masses in water evaporation of the water. The products of the process are are stable and can be stored and transported and can be 70 suitable for use in the production of coatings and cover worked up at any later date, e.g. by a shaping process. ings and for impregnating woven and nonwoven textiles, They generally dry quickly to form dimensionally stable leather, paper, wood, metals, ceramics, stone, concrete, Synthetic resin coatings, but shaping of the products can bitumen, hardboard, straw, glass, procelain, all sorts of also be carried out in the presence of known cross-linking 75 Synthetic resins, glass fibers, for production of antistatic 3,756,992 25 26 The following are examples of methylol compounds Catalysts such as sodium carbonate, potassium carbon which may be used: dimethylol urea, hexamethylol mel ate, ammonia or urotropine may be added to accelerate amine, hexamethylol-melamine methyl ether, tetrameth the reaction between the terminal acylated amino groups ylol acetone, hexamethylol acetone, methylol compounds and the dissolved formaldehyde. The quantity of catalysts and methylol ethers of urea, ethylene urea, methylene should, however, be kept small, especially in the case of diurea, biuret, carbonyldiurea, hexamethylene diurea, cationic products, in order that the stability of the disper acetylene diurea, hydrazodicarbonamide, tetrahydropyr sions produced should not be impaired. imidinone, tetrahydro-1,3,5-oxadiazinone-(4), dicyandi The quantity of water required depends mainly on the amide, acrylamide polymers and methacrylamide poly concentration at which the paste of water in polyurethane mers, formaguanamine, acetoguanamine and benzoguan O which is first formed changed over into a polyurethane/ amine. water dispersion. While this may occur at polyurethane In addition to formaldehyde, higher aldehydes such as concentrations of about 68 percent, in some cases it may acetaldehyde, chloral, crotonaldehyde, acrolein, furfural, not occur until the concentration is 20 percent. The total glyoxal and glutaric dialdehyde, ketones such as acetone, quantity of water required thus amounts to 0.5 to 4 times, methylethyl ketone and cyclohexanone, and their con and preferably 0.8 to 3 times, the quantity of polyurethane. densates with compounds which form aminoplasts or The water should be added at such a rate that it will be mixed condensates with formaldehyde and compounds taken up evenly by the polyurethane mass. The mixing which form aminoplasts, may be used. process may generally be carried out satisfactorily in the In all cases, in order to insure that reaction with the usual stirrer apparatus or stirring tanks with slowly rotat reactive groups -X-NHR occurs, the aqueous solutions ing horseshoe stirrers, provided that the stirring is suffi of such formaldehyde derivatives should contain free for ciently efficient for the high viscosities which occur. Stirrer maldehyde in equilibrium under the reaction conditions. mechanisms which at the same time also insure thorough It is not necessary, however, for this reaction to produce mixing of the material in a vertical direction, e.g. spiral exclusively the methylol-containing groups stirrers, are especially suitable. High speed stirrers are generally less suitable. R CHOH If the polyurethane mass already contains terminal or -X-N methylol groups, for example due to reaction of a pre YoHoH CHOFI polymer which carries NCO end groups with oligomethylol compounds, the presence of formaldehyde during the dis It is possible, within the scope of the invention, for new 30 persing process is not necessary. In such cases, water, if methylol compounds desired together with the quantities of acids or bases R required for neutralization of the potential salt groups, is -X-N stirred into the (potential) polyurethane electrolytes which contain terminal reactive methylol groups. YcH-2-(CH-OH). The spontaneous dispersion of the polyurethane which to be produced by reaction of the reactive groups then takes place is brought about by the combined action -X-NHR with oligomethylod compounds of the built-in ionic groups and the terminal methylol HO-CH-Z-(CH-OH) groupS. In general, the water is first taken up with formation of in which Z is, for example, a radical which is difunctional 40 an almost clear solution. With progressive addition of to hexafunctional towards formaldehyde and n is an Water, a milky white paste is formed which contains the integer from 1-5. Water partly in solution and partly dispersed in the poly Further condensation in which the methylol com urethane (water-in-oil type of dispersion). With further pounds undergo substantially complete reaction, on the addition of water, the paste changes into a polyurethane other hand, must definitely be avoided before formation in-water dispersion. In some cases, this transition only of the dispersion. This is achieved by carrying out the takes place on cooling the dispersion. mixing of the polyurethane mass with the formaldehyde The temperature during the addition of water lies containing aqueous solutions at pH values of preferably between room temperature and 150° C., and preferably between 9 and 4.1 and especially between 7.5 and 5.5. between 50 and 130° C. One may, for example, stir in Furthermore, the stages in the process of the invention approximately the first half of the water at temperatures between the mixing process and the formation of the between 80 and 130° C. and then add more water with dispersion should generally not take longer than about cooling. According to a particularly preferred procedure, two hours. the total quantity of water up to formation of the polyur The quantity of formaldehyde required, in free or ethane-in-water dispersion is added at temperatures of bound form, depends on the quantity of reactive about 100° C. At temperatures above 130° C., it is advan -X-NHR groups present, taking into consideration also tageous to work under excess pressure. the reactive -X-NHR groups present within the chain, If the entire process for the production of the polyure for example when tertiary nitrogen has been quaternized thane mass, or even only the dispersion process, is to be with chloroacetamide. The equivalent ratio of -X-NHR carried out continuously, one may use a special screw to formaldehyde (based on the free formaldehyde) lies apparatus. between 1:0.3 and 1:4, in particular between 1:2 and 1:0.6. Smaller quantities of formaldehyde are disadvan If the resulting dispersion is cooled immediately after it tageous because chain lengthening then does not take has been produced and is then dried at room temperature, place to a sufficient extent even if the conditions are suit the properties of the product are not satisfactory. Strength able for adequate dispersion. Larger quantities of formal 65 and water resistance are low. In order to obtain properties dehyde are generally of no advantage but produce a which are satisfactory for commercial purposes, heat treat strong smell in the dispersion and lead to the release of ment of the products is necessary. This may be carried out large quantities of formaldehyde during drying. before and/or during and/or after shaping of the disper Larger quantities of formaldehyde should, however, sion, Shaping may be carried out, for example, with simul be used, if in the course of the process or before applica taneous drying of the products by removal of water. The tion of the product, additives which are capable of re products can also be produced by a process of coagulation, acting with formaldehyde, e.g. urea, methylene-bis-urea, for example by electrophoretic deposition on an electrode. polyureas, melamine or guanamine, urea-melamine resins In heat treatment before removal of the water from the or urea-phenol resins are added to modify the properties dispersion, the resulting dispersion is exposed for some of the dispersion. 75 time, e.g. for 10 minutes to 48 hours, to a temperature 3,756,992 29 30 and increase resistance finishes, as binders for fleeces, ad the form of powder or fibers or cellulose. The end product hesives, bonding agents, backing agents, agents for ren may contain up to 70 percent of such fillers, based on dering substances hydrophobic, plasticizers, binder, e.g. for the total weight of dry substance, depending on the de cork powder or saw-dust, glass fibers, asbestos, paper sired properties of the products and purposes for which type materials, plastics or rubber waste, ceramic mate they are to be used. rials, as auxiliary agents in textile printing and in the The addition of these substances, may be carried out paper industry, as additives for polymers, as sizing agents at various stages during the production of the dispersions and for finishing leather. and in various forms. The polymers may already be in Powders or pastes which are obtained from suspension cluded during the preparation of the polyurethane dis can be used as additives to polymers such as polyvinyl persions, although they may also be added to the finished chloride, polyvinyl acetate or styrene-butadiene copoly 10 polyurethane suspensions or to pastes or powders pro mers. The powder may, for example, be added to the duced therefrom, in the form of their aqueous emulsions polymers- which are in the solid or molten form, on mix or suspensions, or as powders, so that they act as fillers. ing rollers or in an extruder. Dyes, pigments, plasticizers or additives which affect Alternatively, the products of this invention may, for the flow properties may, of course, also be added. example, be stirred into polymer dispersions or suspen Drying of the products obtained by various methods sions. The properties of the polymers can be significantly of application can be carried out at room temperature or improved by the addition of the polyurethane micro elevated temperature, although melting or fusing of the powders. material should not occur. The drying temperature to be Polyurethane powders can also be used as high grade selected in any individual case, which depends on the fillers for epoxide and polyester resins, the flexibility and chemical composition of the material and, in particular, elasticity of which can be improved. They are also suit its moisture content, the drying time and the layer thick able for use as solvent-resistant binders, in which case ness, can easily be determined by preliminary tests. For the fibers may be of natural origin (cotton, wool) or syn a given heating time, the drying temperature must always thetic origin (rayon, polyamide, polyacrylonitrile). Inor 25 be below the solidification temperature (see below). The ganic fillers (glass, asbestos) may also be bonded with material must on no account become transparent during these binders. drying. Other uses arise from their ability to serve as adhesives, If drying is carried out attemperatures between 10 and as additives to dyes and lacquers to improve their ab 40 C., solidification of the material generally does not rasion resistance, and as lubricant additives. The poly 30 take place. The sheets obtained can generally be crum urethanes present in the form of dispersions are also suit bled by hand and in many cases they are even redis able for use as emulsifiers for the preparation of polymer persible. dispersions, e.g. of polymer dispersions from nonionic poly Solidification is carried out by the application of ele urethanes. Sedimenting dispersions or suspensions, pastes wated temperatures, preferably between 50 and 180° C., and powders prepared from them are especially suitable the particles at the same time undergoing sintering with for use in the production of microporous sheets. mechanical intermeshing or partial fusion of the boundary A great advantage of these dispersions over products of surface as a chemical cross-linking reaction taking place known processes for the production of microporous sheets between the boundary surfaces of the particles. Further is that in the production of the products of the process, excessive sintering or complete fusion is prevented by the shaping can be carried out by conventional industrial 40 cross-linking of the boundary zones, so that the whole methods and using conventional machines. The disper material remains permeated by extremely fine ducts. sions described above can be applied particularly easily Drying and solidification can be carried out simultane as 30 to 70 percent pastes by pouring or application with ously or successively. The solidification temperature of a wiper apparatus. Conversion into the paste form, if predried layers is about 10-30° C. higher than that desired by means of the usual commercial thickeners, 45 of moist sheets. The solidification temperature has to be which are advantageously added in quantities of 1 to 10 increased with decreasing water content in order to percent to adjust the paste to the desired viscosity, reduces achieve comparable results. The length of time for which the sedimentation rate, according to the concentration, and the foil material should be exposed to the elevated tem causes smooth, uniform flow of the masses. Highly con perature, the thickness of the foil and the pressure applied, centrated pastes having a solids content of about 50 to 50 if desired, for example, by hot rollers used for solidifica 70 percent can be kept for days without phase separation. tion, are other important factors which strongly influ The suspensions or pastes are preferably applied to a ence the microporosity, permeability to water vapor and porous support which then remains bonded to the finished physical properties of the products according to the in product, e.g. woven or nonwoven textiles or fibers mats, vention. felts, fleeces, including paper fleeces, foam resin foils or 55 Sheets measuring 100 to 400u in thickness can be sin split leather, which bring about immediate solidfication of tered by short exposure to elevated temperatures, for ex the coating of gel particles by their suction effect. The ample, for a few seconds, in the case of foils which are product is then dried at elevated temperature and pressed, substantially free from water, to a few minutes in the case if desired, causing solidification of the globular structure of sheets which are still slightly moist. The temperature of the coating. Alternatively, drying may be carried 60 employed here may be considerably above the solidifica out on smooth, porous or nonporous materials, e.g. metal, tion temperature otherwise required for longer drying glass, cardboard, ceramic materials, sheet steel, silicone times. rubber or aluminium foil, and the finished sheeting can The finished sheets according to the invention are milky then be lifted off and used as such or applied to a sub and opaque or even as is usual, completely white having strate, generally a porous substrate, by the reversing proc a warm, pleasant hand, good tensile strength and low ess by bonding with adhesive, flame backing or calender abrasion. They are insoluble in solvents, and are frequent ing. The application by the reversing process may be car ly even insoluble in hot dimethylformamide. The perme ried out at any time. ability to water vapor is distinctly higher than that of The properties of the products can be modified by the the corresponding homogeneous materials and in most inclusion of active or inactive fillers, for example, poly 70 cases corresponds to that of natural leather. ethylene, polypropylene, polyvinyl acetate, ethylene-vinyl A distinct morphological structure can be seen under acetate copolymers which may be (partly) saponified and/ the optical microscope. or grafted with vinyl chloride, styrene-butadiene copoly The sheets can then be covered with a finish to increase mers, ethylene (graft) copolymers, carbon black, silicic the resistance of their surface. Aqueous dispersions and acid, asbestos, talcum, kaolin, titanium dioxide, glass in 5 solutions are again preferred for this purpose. 3,756,992 31 32 The products of the process can be used in many differ are spherical with diameters between 200 and 500 m.pl. ent ways, e.g. as coatings of all types which are permeable They are largely combined into aggregates of 3-6 pri to air and water vapor, and as damping materials for mary particles each. absorbing sound and mechanical vibrations. Molecular weight increase on storage (see above ex For example, tent sheets, rain coats, bags, belts, shoes, periment): upholstery material, car linings, and wall papers can be produced from these sheet materials. Very hard polyurethanes obtained from dispersions with After very small particles and sols are suitable for use as stov 0 days 7 days 18 days 42 days ing lacquers and in some cases even as air drying lacquers. O pH 5-6, Seconds------2 1.2 1, 6 11.7 They combine the properties of great hardness and elas pH 2-3, Seconds------1.3 2, 3 4, 2 39.5 ticity with high gloss and, when used with aliphatic diiso cyanates, good stability to light and weathering. Cloudy. The invention will be further illustrated by the follow ing examples in which parts are by weight unless other EXAMPLE 3 wise specified. Reactants EXAMPLE 1. 500 parts (0.303 mol) polyester of phthalic acid, adipic Reactants acid and ethylene glycol (1:1:2.3), molecular weight 500 parts (0.303 mol) of a polyester of phthalic acid, 20 1650 (PEP) adipic acid and ethylene glycol (1:1:2.3), molecular 50 parts (0.420 mol) of N-methyldiethanolamine (MDA) weight 1650 (PEP) 52 parts (0.870 mol) urea 50 parts (0.420 mol) of N-methyldiethanolamine (MDA) 194.5 parts (1.158 mol) 1,6-hexanediisocyanate 52 parts (0.870 mol) urea (U) 19.6 parts (0.21 mol) chloroacetamide 201 parts (1.158 mol) of toluylene diisocyanate, isomeric 25 12.6 parts (0.21 mol) acetic acid ratio 65:35 (T65) 129 parts by volume (1.25 mol) 30 percent aqueous form 39 parts (0.420 mol) chloroacetamide aldehyde 258 parts by volume (2.5 mol) 30 percent aqueous form 30 parts by volume ethyl glycolmonomethyl ether acetate aldehyde 1400 parts by volume Water 30 parts by volume ethylene glycolmonoethyl ether ace 30 Method tate (GMA) The same as in Example 1, the acetic acid being added 1150 parts by volume water together with the first portion of water. An opaque, 32 Method percent sol was obtained, pH=5. Samples of the original dispersion and of a dispersion which had been adjusted to PEP, MDA and U are introduced into the reaction ves 35 sel at about 60° C. and T 65 is added within about 1 pH 2-3 with tartaric acid are dried at room temperature minute. The temperature rises to about 111 C, and at for about 24 hours and for half an hour at about 80 C. the same time there is a sharp increase in viscosity. When and then treated with distilled water. For results see table. the reaction mixture has been heated to about 120° C., uull-les--alar the temperature spontaneously rises to about 133 C. 40 After 1 hour's After 24 hours' (urea reaction). The chloroacetamide is then added and treatment with treatment with washed down with GMA. The temperature is then kept Water Water for a further 10 minutes at about 130 C, the reaction pH 5, 24 hours at room Dissolved.------Dissolved. temperature. mixture is left to cool to about 100 C. About 1,000 pH 2-3, 24 hours at room Unchanged.------Clear, SWelled. parts by volume of water are added dropwise within about temperature. 45 pH 5, S; at 80 C------White bloon.------Heavy white bloon. 45 minutes, the temperature being meanwhile kept at pH 2-3, 30' at 80°C.------Unchanged.------Clear, slightly SWelled. 100-110° C. An opaque, thick sol is obtained which after Ull-les-an-e-r"." cooling for about 20 minutes yields a liquid, slightly yellow, 41.5 percent latex of low viscosity. The particles are predominantly spherical, having a diameter between EXAMPLE 4 50 and 120 mu, 50 Reactants Part of the dispersion is adjusted to pH 2-3 with tar 500 parts (0.303 mol) of a polyester of phthalic acid, taric acid. adipic acid and ethylene glycol (1:1:2.3) molecular About 10 parts samples of the original dispersion (pH weight 1650 (PEP) 5-6) and of the acidified dispersion are dissolved in about 55 15 parts (0.126 mol) MDA 25 parts by volume of tetrahydrofuran at intervals of 26 parts (0.428 mol) urea several days, and the outflow viscosity from a 2 ml. pipette 108 parts (0.643 mol) 1,6-hexanediisocyanate which has been cut off at the bottom is measured in 7 parts (0.075 mol) chloroacetamide seconds. 3 parts (0.061 mole) acetic acid 60 129 parts by volume (1.25 mol) 30 percent aqueous After formaldehyde 0 days 3 days 10 days 21 days 45 days 30 parts by volume ethylene glycol monomethylether pH 5-6, Seconds...-- 0.6 0.8 1,2 1.2 1.0 acetate pH 2-3, Seconds.------0.6 1.0 2.5 5.0 50 830 parts by volume water 65 Slightly yellowish, elastic, fairly hard foils are obtained Method on drying the acidified dispersions. As in Example 3. After the addition of water at 130 C., a coarse particled latex is obtained which becomes EXAMPLE 2 thicker on cooling and shows rheopectic characteristics. Reactants and method as above, except that only 86 70 Yield 1700 parts, solids 40 percent, pH 5-6. parts by volume (0.85 mol) of 30 percent aqueous form The foils which are obtained by drying at room tem aldehyde and about 900 parts by volume water are used. perature the dispersions, acidified to pH 2-3, are clear, The viscous dispersion obtained after the addition of glossy and soft and have good water resistance. The prop water thickens when cooled with stirring. The dispersion erties are substantially improved by after-heating at has a concentration of 46 percent. The primary particles 75 120 C, 33 3,756,992 34 EXAMPLE 5 EXAMPLE 7 The same procedure is employed as in Example 3 but Reactants only using 32.25 parts by volume of 30 percent aqueous 500 parts (0.37 mol) of a polyester of phthalic acid and formaldeyhde. ethylene glycol (molecular weight 1350) The resulting latex is very finely divided, thick and 30 parts (0.252 mol) MDA slightly thixotropic. After acidification to pH 3, soft, 60 parts (1.000 mol) urea slightly sticky thermoplastic foils are obtained on drying 188 parts (1.122 mol) of 1,6-hexanediisocyanate at about 80 C. The latex is suitable for use as an adhe 21 parts (0.224 mol) chloroacetamide SW 1.7 parts (0.028 mol) acetic acid 10 EXAMPLE 8 129 parts by volume (1.25 mol) 30 percent aqueous The same procedure was employed as in Example 3 formaldehyde but using about 41 parts of thiourea instead of the urea, 680 parts by volume water and about 64.5 parts by volume of 30 percent aqueous 20 parts by volume ethylene glycol monomethyl ether formaldehyde. A highly fluid, yellow latex which showed acetate (GMA) no Tyndall effect was obtained. After acidification with Polyester, MDA and urea are introduced into the re tartaric acid to pH 2-3, pale yellow, transparent, soft, action vessel at about 85° C. and 1,6-hexanediisocyanate somewhat elastic and slightly sticky foils were obtained is rapidly added. The reaction starts after two minutes. by drying the latex at about 80° C. The temperature is prevented from rising above about 20 EXAMPLE 9 150 C. by cooling. Solid chloroacetamide is added at The same procedure is employed as in Example 3 but about 130 C. to the very viscous mass, and washed down using about 40 parts of methyl urea instead of urea and with GMA. The reaction mixture is then stirred for about about 64.5 parts by volume of 30 percent aqueous form 30 minutes at about 130° C. and a solution of acetic acid aldehyde. in about 80 parts by volume of water is added dropwise 25 An opaque, 30 percent sol is obtained which dries at in the course of about 13 minutes to the highly viscous, elevated temperatures to form clear, soft, elastic coat clear melt, the melt remaining clear. The formaldehyde ings. The water resistance is improved by previously solution is then added dropwise at about 90° C. in the course of about 20 minutes and the remaining water is acidifying the latex and drying at elevated temperature. then added dropwise in the course of about 50 minutes 30 EXAMPLE 10 at about 130° C. A relatively coarse disperse thick liquid The same procedure is employed as in Example 3 but latex is obtained; the viscosity of the latex decrease on using about 47 parts of N, N'-dimethylurea instead of cooling. The concentration of the dispersion is 52 percent, urea and about 64.5 parts by volume of aqueous 30 per pH 5-6. cent formaldehyde. If the acidified latex is painted on wood or glass, high 35 An opaque, 42 percent sol which dried at about 100° gloss, clear, colorless lacquer coats are obtained. After a C., to form very soft, very sticky masses is obtained. heat treatment at 80 C. they are very hard and resistant to Wear. EXAMPLE 1.1. EXAMPLE 6 The same procedure is employed as in Example 3 40 but using about 48 parts of methylthiourea instead of Reactants urea and about 64.5 parts by volume of 30 percent aqueous formaldehyde. 500 parts (0.281 mole) of a polyester of phthalic acid An opaque, 41 percent sol which dries at 100° C. to and ethylene glycol (molecular weight 1350) form Soft, thermoplastic coatings is obtained. 52 parts (0.780 mol) urea 45 190.5 parts (1.136 mol) of 1,6-hexanediisocyanate EXAMPLE 12 53.5 parts (0.278 mol) of citric acid Reactants: 29.2 parts (0.278 mol) of diethanolamine 64.5 parts by volume (0.63 mol) of 30 percent aqueous 500 parts of a polyester of phthalic acid, adipic acid and formaldehyde 50 ethylene glycol (molecular weight 1650) (PEP)) 50 parts N-methyldiethanolamine 1080 parts by volume water 52 parts urea The diisocyanate is added to the polyester and urea at 194.5 parts 1,6-hexanediisocyanate about 75 C. and the mixture is heated. An exothermic re 25 parts acetic acid - s action sets in at about 130° C. and the temperature rises 55 129 parts by volume 30 percent aqueous formaldehyde to about 151 C. After the reaction has died down citric 1500 parts by volume water acid at about 120° is added. A vigorous reaction immedi Method ately sets in, the reaction mixture becoming yellow and undergoing foaming. The temperature first drops to about The same as in Example 3, without the use of mono 90° C. and then rises to about 120° C. A solution of di 60. chloroacetamide and ethylene glycol monomethylether ethanolamine in about 80 parts by volume of water is acetate. About 1,000 parts of the resulting dispersion then added over a period of 3 minutes, followed by the are diluted with about 1,000 parts of water. The resulting addition of about 64.5 parts by volume of aqueous form 20 percent suspension is coarsely disperse and sediments aldehyde over a period of about 4 minutes, and this in within 12 hours. However, it can be redispersed at any turn is followed by the addition of about 750 parts by 65 time simply by shaking. A polyurethane paste which has volume of water over a period of about 15 minutes. All a concentration of about 60-70 percent and which can these substances are added at about 100° C. A further be diluted again with water at any time is obtained by 250 parts by volume of water are then added at about pouring off the supernatant water. 130° C. over a period of about 23 minutes. After cooling, If the paste, acidified to pH 2-3, is painted on a textile a white, viscous latex which shows slightly rheopectic 70 support and dried at 80 C., a mat, soft, elastic foil which properties and which has a good consistency for painting has good resistance to water is obtained, is obtained. - EXAMPLE 13 The latex is painted on a textile support and dried. After a heat treatment of 100-120. C., the coating is About 1,000 parts (0.6 mol) of an ester of adipic acid, resistant to water and organic solvents. . . . ; 75 s hexane diol, and neopentylglycol is reacted for about one 3,756,992 35 36 hour at about 130 C, with about 201 parts of 1,6- EXAMPLE 1.5 hexanediisocyanate, and about 107 parts of dimethyl Reactants aminoethanol are then added at about 80 C. The reac tion mixture is kept for another 30 minutes at about 130 500 parts (0.281 mol). PEP (as in Example 1) C. and a pale, viscous polyurethane lacquer which has an 30 parts (0.252 mol) MDA average molecular weight of about 2,200 and which con 32 parts (0.534 mol) urea tains terminal amino groups is obtained. 1345 parts (0.800 mol) 1,6-hexamethylenediisocyanate About 218 parts of the above resin are reacted with 14 parts (0.150 mol) chloroacetamide about 20.6 parts of monochloroacetamide for about 1 6 parts acetic acid hour at about 120° C. and a polyurethane resin which 112 parts tartaric acid contains quaternary ammonium groups and terminal O 64.5 parts by volume of 30 percent aqueous formaldehyde carbonamide groups is obtained. 1050 parts by volume water About 30 parts by volume of water, followed by about This procedure is the same as in Example 3. The 80 parts by volume of 30 percent aqueous formaldehyde quantity of tartaric acid indicated above is added to the and lastly about 300 parts by volume of water are added cold latex, the pH thereby being adjusted to 2-3. The to this product at about 100° C. A 42 percent latex acidified latex is heated to boiling for about 50 minutes which dries to form a soft, elastic foil at about 120 C. for cross-linking to take place. A sample taken after this after acidification to pH 3, is obtained. time is no longer soluble in tetrahydrofuran, but forms a jelly-like mass therein. EXAMPLE 14 After cooling, a highly fluid, very finely divided, 32 The same procedure used as in Example 13 for prepar percent latex is obtained which dries at room temperature ing a polyurethane resin which has terminal tertiary to form nonsticky foils of high tensile strength which have amino groups, but using about 151 parts of 1,6-hexanedi a dull gloss. isocyanate and about 53 parts of dimethylaminoethanol. EXAMPLE 16 The resin formed has an average molecular weight of 25 About 500 parts of PEP (see Example 15) are reacted 4,000. with about 71 parts of 1,6-hexamethylenediisocyanate for About 200.5 parts of this resin are reacted with about about 1 hour at about 130° C. about 18 parts of N 10.3 parts of monochloroacetamide for about 1 hour at methyldiethanolamine and, 5 minutes later, another 25.5 about 120° C. About 10 parts by volume of water, about parts of 1,6-hexamethylenediisocyanate and about 17 40 parts by volume of 30 percent aqueous formaldehyde 30 parts of urea, are added at about 80° C. The reac and about 530 parts by volume of water are added to tion mixture is then stirred at about 130° C. for about this at about 100° C. A 28 percent latex which dries to 25 minutes, about 5 parts of chloroacetamide in about form a soft, elastic foil at about 120° C. is obtained 10 parts by volume of ethylene glycol monomethylether after acidification to pH 3. are added, and the mixture is then stirred for another Comparative test 15 minutes at about 130 C. The following are now added in succession: For comparison, a polyurethane which has terminal About 7 parts of glacial acetic acid in about 120 parts by volume of water at about 90° C. in the course of about 40 10 minutes, about 80 parts by volume of 30 percent CH-CHO aqueous formaldehyde at 90° C. in the course of 6 \ minutes; about 250 parts by volume of water at about -x-N CH-CHOH 130 C, in the course of about 15 minutes and about 500 parts by volume of water at about 110° C. in the course of about 25 minutes. The resulting dispersion is adjusted is prepared and is dispersed with an aqueous formalin 45 to a pH of 4 with about 20 parts by volume of 30 percent solution. tartaric acid, which results in thickening of the reaction To prepare this polyurethane, about 194.5 parts of 1,6- mixture, and the reaction mixture is then stirred for one hexamethylenediisocyanate are added to about 500 parts further hour at about 110° C. until a 10 parts sample of the polyester mentioned in Example 1 and about 50 forms a jelly-like mass with 50 parts by volume of parts of N-methyl-diethanolamine at about 68 C. An 50 tetrahydrofuran. A relatively coarse latex is obtained exothermic reaction sets in immediately, the temperature from which a serum separates at the top in the course rising to about 135° C. The reaction mixture is then of time and which then forms a thick paste which has a stirred for a further 20 minutes at this temperature, and good consistency for painting purposes. The paste can the prepolymer is poured with vigorous stirring into about be easily diluted with water at any time. 91.5 parts of diethanolamine. This is then washed down 55 A soft, flexible, water resistant and mechanically very with about 30 parts by volume of ethylene glycol mono methylether, the temperature is kept at about 130 C, strong foil is obtained on drying at about 80 C. about 39.2 parts of monochloroacetamide are added, and EXAMPLE 17 the reaction mixture is stirred for a further 30 minutes at about 135° C. The following are then added in Suc 60 About 500 parts of a polyester of phthalic acid and cession: about 150 parts by volume H2O over a period ethylene glycol, of OH number 48, about 25.4 parts of of about 50 minutes at about 90° C., about 129 parts by N-methyldiethanolamine and about 26 parts of urea are volume of 30 percent aqueous formaldehyde at about mixed with about 108 parts of 1,6-hexamethylenediiso 95° C., over a period of about 40 minutes, and about 750 cyanate at about 85 C. The temperature rises to about parts by volume water at about 130 C. over a period 65 122 C. due to the polyaddition reaction which sets in of about 50 minutes. After cooling, a very thick, colloidal at once. The temperature is then raised to about 130° C. solution is obtained, which is diluted with 1,100 parts by and about 20 parts of chloroacetamide in about 20 parts volume of water. by volume of ethylene glycol monomethyl ether are added. A completely stable, aqueous-colloidal polyurethane so After stirring for about 30 minutes at 100-120° C., about lution is obtained. A sample is adjusted to pH 2-3 with 70 130 parts by volume of 30 percent aqueous formaldehyde tartaric acid, poured on a support and afterheated for are added dropwise in the course of about 20 minutes. about 30 minutes at about 80° C. No foil is obtained. About 1050 parts by volume of water are stirred into the Instead a soft, sticky mass which dissolves in water is viscous, almost clear mass in the course of about 50 min obtained. In other Words, no polycondensation to form utes and a finely divided dispersion is formed. This is a high molecular weight resin has taken place. 5 adjusted to pH 4 with about 20 parts by volume of 30 3,756,992 37 38 percent tartaric acid and then stirred for a further 30 sol of substantially equal properties as that of Example 20 minutes at about 120° C. A sample is soluble in tetrahy is obtained. drofuran, forming a clear solution. The 37 percent lacquer EXAMPLE 22 is eminently suitable for use as a stoving lacquer. It The process is carried out as in Example 20, however, dries at room temperature within a short time to form 5 before dispersion 60 g. of 30% formalin are dissolved in completely nonsticky, touch-resistant high gloss coatings 1100 g. of water and this solution is added within 30 min which are rendered extremely hard, scratch-resistant, firm- . utes after the addition of the phosphoric acid. A sol of ly adhering and resistant to water and organic solvents by substantially equal properties as that of Example 20 is Subsequently heating them at about 80 C. obtained. EXAMPLE 1.8 - O EXAMPLE 23 About 193.5 parts of 1,6-hexanediisocyanate are added : The reaction is carried out as in Example 20, however, at about 70° C. to about 500 parts (0.298 mol) of a poly- . while using 195 ml. of 1 n-hydrochloric acid instead of ester of adipic ester, hexane diol and neopentyl glycol, phosphoric acid. A highly fluid 41% white latex is ob about 50 parts of N-methyldiethanolamine and about 54 5 tained which is suitable, for example, in the coating of parts of urea. The reaction mixture is heated until, be textiles. tween about 120 and about 130 C., an exothermic reac EXAMPLE 24 tion sets in. The temperature should not be allowed to ex The reaction is carried out as in Example 20, however, ceed about 150° C. About 20 parts of monochloroacet while using 12 g. only instead of 25.g. of 85% ortho amide are then introduced and, after about 30 minutes, phosphoric acid. A highly fluid white latex is obtained. first about 12.6 parts of glacial acetic acid in about 150 Solids content: 39.5%. This latex can also be produced parts by volume of water and then about 50 parts by vol by adding a 31% formalin solution immediately after or ume of 30 percent aqueous formaldehyde solution are before the addition of phosphoric acid. After the addi added. The reaction mixture is stirred for about 75 min tion of the two components the total quantity of water is utes at about 100° C. when the smell of formaldehyde 25 added. Instead of N-butyldiethanolamine the equivalent will have practically completely disappeared. About 1,200 quantity of N-methyldiethanolamine or N-methyldiiso parts by volume of water are stirred into the clear, viscous solution over a period of about one hour. A very finely propanolamine can be added. divided, opaque, thick liquid latex is formed. This is ad EXAMPLE 25 justed to pH 4 with about 20 parts by volume of 30 per 30. (a) Prepolymer cent tartaric acid solution, about 30 parts by volume of 30 percent aqueous formaldehyde solution are added, and 2000 g. (0.760 mol) of adipic acid diethylene glycol the reaction mixture is stirred for about 2 hours at about polyester and 254 g. (1.51 mol) of 1,6-hexamethylene di 100° C. isocyanate are heated to 130° C. for 2 hours. The resulting dispersion yields highly elastic, nonsticky (b) Dispersion and light stable films. To 304 g. of the prepolymer there is added at once at EXAMPLE 19 80 C. a solution of 31.6 g. of maleic acid ureide and 14 g. 185.6 g. of toluylene diisocyanate (isomer mixture of potassium hydroxide in 144 g. of a 20% taurine-sodium 65:345) are added to 500 g. (0.214 mol) of an adipic 40 solution in water (90° C). 60 ml. of a 30% formalin acid butane diol polyester, 50 g. of N-methyl diethanol solution are added within 3 minutes and subsequently 600 amine and 52.3 g of urea at 75 C. within 2 minutes. ml. of water within 8 minutes. A highly fluid white latex is The temperature rises to 140 C. within 10 minutes. Into obtained which is adjusted to pH 4 by the addition of 30 the solution are introduced 19.6 g. of monochloroacet ml. of a 30% tartaric acid solution. Upon drying the latex amide and 30 ml of glycol monomethyletheracetate and, and heating at 130° C. soft elastic solvent-resistant films after 30 minutes, first 12.6 g. of glacial acetic acid in 150 45 are obtained. ml. of water, then 100 ml. of a 30 aqueous formaldehyde EXAMPLE 26 solution within 15 minutes. 1500 m. of water of 90° C. 250 g (0.162 mol) of phthalic acid ethylene glycol are added dropwise to the turbid viscous solution at 100 polyester and 12.7 g (0.107 mol) of N-methyldiethanol to 110° C. within 60 minutes. The yellowish coarse dis 50. amine are reacted at 130° C. for 30 minutes with 110 g. persion is subsequently diluted with 1600 ml, of water of (0.635 mol) of 1,6-hexamethylene diisocyanate (NCO/ 20° C. There is obtained a sedimenting, redispersible dis CH-ratio 2.44). The mixture is then stirred at 130° C. persion having particles of a diameter between about 0.2 for another 30 minutes with 33 g. of urea (NCO/urea and 0.8 mm. Upon drying the dispersion on porous plates ratio 1.4). Quaternization is effected with 10 g. of chloro the polyurethane is obtained in form of a powder. 55 acetamide at 130 C, within 30 minutes. The mixture is allowed to cool to 110° C., a 100 ml. of a 30% aqueous EXAMPLE 20 formalin solution is added; this is followed by stirring at 122 g of hexamethylene diisocyanate are added at 80° 110° C. for another 30 minutes and 500 ml of water of C. to 500 g. (0.284 mol). PEP (see Example 1), 32.2 g of 90° C. are then added. The resulting highly fluid, rela N-butyl diethanolamine and 20 g. of urea and the mixture 60 tively coarsely dispersed latex is acidified with 10 ml. of is reacted at 130 C. for 60 minutes. At 90° C. successive a 30% tartaric acid solution, cooled down and mixed with ly are added 25 g. of 85% orthophosphoric acid in 50 g. 30 g. of hexamethylene melamin pentamethylether. of water within 5 minutes, 500 g. of water within 20 min The latex dries at room temperature to yield glossy utes, 60 g. of 30% formalin within 4 minutes and 400 g. coatings which, upon stoving at 120 to 150° C., are finally of water within 40 minutes. There is obtained a 41% reacted to yield products of high surface hardness. aqueous thickly sol which has a pH-value of 3 and dries at room temperature to yield a soft transparent sheet. By after-heating at 50° C. (60 minutes) or 130° C. (10. EXAMPLES 27–38 minutes) the resistance to water and organic solvents The reactions are carried out analoguous to Example is increased. . . . . O 3 with the following components. EXAMPLE 21 GO Sample in tetrahydrofurane, clearly soluble : The reaction is carried out as in Example 20, however, (2) Sample in tetrahydrofurane, turbid and highly viscous after the addition of the first 500 g. of water, a solution PEP: adipic acid-phthalic acid-ethylene glycol polyester of 60 g. of 30% formalin in 600 g. of water is added. A 75. (1:1:2,2)

3,756,992 41 42 8. The process if claim 2 wherein the heat treatment is conducted after the water is removed. 2 2. als 9. The process of claim 2 wherein the heat treatment is conducted before, during and after the water is N N tN --l removed. 2 10. The dispersion of claim 1 wherein the polyurethane Z represents polyelectrolyte has been prepared from an organic diiso cyanate and compounds containing reactive hydrogen atoms having a molecular weight of 50-8000, said poly urethane polyelectrolyte having a molecular weight of -NHR, -{ X or R. 2000 to 10,000, containing 8 to 80 milliequivalents per R represents: 100 grams of salt groups or groups capable of salt forma a hydrogen atom or tion and subsequently converted into Salt groups, having an alkyl radical with 1 to 4 carbon atoms, a viscosity from 100 to 1000 poises, said polyurethane which may be substituted by OH, OCH3, 5 polyelectrolyte being dispersed by mixing with water at OCH, CC1, COOH or SOH or 50 to 130° C. an alkenyl radical with 1 to 4 carbon atoms 11. The dispersion of claim 1 wherein the group which may be substituted by OH, OCH3, -X-NR-CHOH is an -NH-CO-NH-CHCH OCH5, CCl3 COOH or SOH, group. which alkyl or alkenyly radical may 20 12. The dispersion of claim 1 wherein the polyurethane also be part of a heterocyclic 5-mem polyelectrolyte is prepared using polar group forming ur bered or 6-membered ring having 1 polar group containing chain-lengthening agents. to 3 hetero atoms selected from the 13. The dispersion of claim 1 wherein the polyurethane group consisting of nitrogen, oxygen polyelectrolyte is prepared using polar group forming or and sulphur which heterocyclic rings 25 polar group containing organic compounds bearing an are selected from those in which no OH- or -NH-group and a -NH-CO-NH2 group. hetero atom is directly linked with an 14. The dispersion of claim 1 wherein the polyurethane other hetero atom or R represents CN, polyelectrolyte is prepared by addition of polar group CO-R', SOR' in which R' may forming or polar group containing moniisocyanates con represent an alkyl, alkenyl, alkoxy or 30 taining tertiary amino, sulfide or reactive halogen groups carbalkoxy radical having to 4 carbon to non-ionic polyurethanes. atoms, and 15. The dispersion of claim 1 wherein the polyurethane (f) the total quantity of water is 0.5 to 4 times the polyelectrolyte is prepared by addition of compounds quantity of said polyurethane electrolyte. bearing polar group forming or polar group containing 35 agents and at least one -OH, -SH-, -NH-, or 2. A process for the production of high molecular SCl-group to non-ionic polyurethanes bearing reactive weight polyurethanes which comprises heating the dis unsaturated double bonds in the chain. persion of claim 1 at 25 to 200° C. and removing the 16. Process of claim 2 characterized in that the poly Water. urethane dispersion is adjusted to a pH-value between 3. The process of claim 2 wherein said heating is in 40 the range of 70 to 150° C. 4.2 and 2 prior to or during the heat treatment. 4. The dispersion of claim 1 wherein the polyurethane polyelectrolyte is prepared by reacting formaldehyde with References Cited a prepolymer containing terminal groups of the formula UNITED STATES PATENTS 45 3,384,606 5/1968 Dieterich et al. ----- 260-841 3,087,912 4/1963 Wagner et al. ------260-841 5. The dispersion of claim 4 wherein said formalde DONALD E. CZAJA, Primary Examiner hyde is reacted with said prepolymer in an aqueous solu M. J. WELSH, Assistant Examiner tion at pH values between 9 and 4.1. 50 6. The process of claim 2 wherein the heat treatment U.S. C. X.R. is conducted before the water is removed. 117-123 D, 124 E, 126 132 C, 138.8, 142, 148, 155 R; 7. The process of claim 2 wherein the heat treatment 156-331; 260-2.5 AM, 37 N, 29.2 TN, 77.5 AM, 858 is conducted while the water is removed.