3,388,087 United States Patent Office Patented June 11, 1968 2 3,388,087 is then reacted in solution with a monofunctional alkyla AQUEOUS DESPERSIONS OF QUATERNIZED tion agent in case (a), and with a tertiary amine in cases POLYURETHANES (b) and (c). By organic polyol is meant a compound Dieter Dieterich and Otto Bayer, Leverkusen, and Julius 'containing a plurality of hydroxyl groups which are pref Peter, Oderathal, Buchmuhle, Germany, assignors to erably alcoholic hydroxyl groups. There is thus produced Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, 5 a reaction product, in solution, from a polyhydroxyl com Germany, a German corporation pound and a polyisocyanate, if desired with concurrent No Drawing. Filed Oct. 23, 1963, Ser. No. 318,197 use of a chain extender, which product contains groups Claims priority, application Germany, Oct. 26, 1962, which are capable of quaternization in at least one of F 38,153 the components. By this quaternization process, materials 6 Claims. (C. 260-29.2) O are obtained in which salt-like quaternized and organo philic molecule segments alternate with one another, the organophilic segments having a chain length of at least ABSTRACT OF THE DISCLOSURE 50 atoms. The generally rubber-like reaction products are Aqueous dispersions of quarternized polyurethane com quaternized in solution, whereupon an elastic cross-linked positions are prepared by making an organic solvent so Synthetic plastic is formed after suitable removal of the solvent. lution of the quarternized polyurethane and then replac The polyhydroxyl compounds are preferably predom ing the polyurethane with water to get the dispersion. inately linear and preferably have a molecular weight of 20 about 400-about 10,000 most advantageously 1,000-3,000. This invention relates to plastics and more particularly Included are for example polyethers, polyesters, polyacet to plastics which contain the urethane linkage and a als, polyester amides and polythioethers. Examples of method of producing cross-linked plastics from polymers polyethers are the polymerization products of tetrahy of polyols and organic polyisocyanate. drofuran, propylene oxide and ethylene oxide, as well as It is known to treat compounds of high molecular mixed or graft polymerization products. It is also possi weight, more especially polyurethanes, which contain basic ble to start from homogenous or mixed polyethers which nitrogen atoms, with polyfunctional peralkylation agents, may be obetained by condensation of 1,6-hexanediol, 2 and thus to convert them with simultaneous cross-linking methyl-1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and into polyguaternization polymers. The concurrent use of the like, perhaps with addition of about 10-about 30 per monofunctional quarternizing agents has resulted in an in 30 cent of lower glycols such as ethylene glycol, propylene crease in solubility in hydrophilic media (German patent glycol and the like. Ethoxylated and propoxylated (or specification No. 880,485). mixed alkoxylated) glycols may also be used. If the poly The increase in the hydrophilic nature of a substance ether is to contain the quaternizable group, then alkoxyl of high or low molecular weight by monofunctional qua ated and more especially propoxylated glycols with ter ternization is generally known and is widely used. How 35 tiary amino groups, such as propoxylated methyl dietha ever, since a cross-linking or lengthening of the chain is nolamine or alkoxylated primary amines (for example not effected just by quaternization with monofunctional alkoxylated aniline, toluidine and hydrazine) are men alkylation agents, the concurrent use of polyfunctional al tioned as examples. In this case, each polyether molecule kylation agents or other types of cross-linking agents, for contains a quaternizable nitrogen atom. example based on urea formaldehyde, has hitherto been 40 Among the polythioethers, there are more especially to advised for the production of cross-linked, and thereby be mentioned condensation products of thiodiglycol with Water-insoluble, elastic non-tacky materials. In order to itself or with other glycols, among which can also be those exclude premature cross linking, this generally requires which contain tertiary amino groups (e.g. dihydroxy the use of binary system and/or an after-treatment for ethylaniline). example by the action of an increased temperature to 45 As polyacetals, there are to be mentioned more espe cause cross-linking. cially the water-insoluble types of hexanediol and formal It is, therefore, an object of this invention to provide dehyde or hexanediol and divinyl ether, as well as of cross-linked plastics. Another object of this invention is to 4,4'-dihydroxyethoxy diphenyl dimethyl methane and for provide an improved method of making polyurethane maldehyde. plastics. Still a further object of this invention is to pro 50 Polyesters and polyester amides which are obtained vide improved polyurethane plastics which are solutions or from polyhydric alcohols such as ethylene glycol and the dispersions of polygulaternized compounds. A still fur like and polycarboxylic acids such as, adipic acid and the like, perhaps with concurrent use of diamines such as ther object of this invention is to provide improved cross ethylene diamine and the like and amino alcohols such linked elastic non-tacky water-soluble materials prepared as ethanol amine and the like are also to be referred to. from predominately linear polyguaternized polyurethanes. 55 Tertiary amino groups can be incorporated just as well A further object of the invention is to provide elastic syn as quaternizable chlorine atoms into these polyesters. thetic plastics, more especially foils, coatings and adhe It is also possible to start from those polyhydroxyl sion promotors, from solutions based on polyhydroxyl compounds which already contain urethane or urea compounds, polyisocyanates and possibly chain extenders groups. The polyhydroxyl compounds can be readily mixed containing reactive hydrogen atoms. 60 with one another even those with or without quaternizable The foregoing objects and others which will become ap groups. parent from the following description are accomplished in Suitable as organic polyisocyanates and preferably or accordance with the invention, generally speaking, by pro ganic diisocyanates are, for example, all aliphatic and aro viding a plastic prepared by a process which comprises matic diisocyanates, also those known as being highly reacting an organic polyol with an organic polyisocyanate, 65 active, such as naphthalene-1,5-diisocyanate, diphenyl-4, and possibly a chain extender to prepare an intitial prod 4-methane diisocyanate, dibenzyl-4,4'-diisocyanate, phen uct, at least one of the components of the initial product ylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, toluyl contains at least (a) a tertiary nitrogen atom, (b) a halo ene diisocyanates such as 2,4- and 2,6-toluylene diiso gen atom or (c) an R-SO-O-group (in which R rep cyanate and the like. Less reactive diisocyanates such as resents an organic radical preferably having 1 to 12 car 70 tetra-alkyl diphenylmethane diisocyanate, for example, 2, bon atoms as an alkyl or aryl radical) said initial product 2,3,3'-tetramethyl diphenyl methane-4,4'-diisocyanate, di 3,388,087 3 4. cyclohexyl methane diisocyanate and aliphatic diisocya cross-linking. If a bifunctional quaternizing agent is ad nates such as hexamethylene diisocyanate offer the advan ditionally used, this is generally not to exceed about 0.2 tage of yielding reaction products with a substantially to about 0.8 percent of the weight of the polyurethane com linear structure. position which is in solution. The quaternizing agent or The quaternizable group can also be contained in the the mixture of quaternizing agents can be simply intro polyisocyanate. Polyisocyanates of this type, which can duced into the solution, possibly even in dissolved form. be mixed with the simple diisocyanates, can be obtained by It is quite possible for the solvent to be mixed from reacting 2 mols of one of the aforementioned diisocya the outset with water, but care should be taken that the nates with methyl diethanolamine, butyl diethanolamine, water which is present does not restrict the solubility of N,N-dihydroxyethyl aniline, N,N-dihydroxyethyl toluidine the polyurethane composition. After effecting quaterniza and the like. Chain extenders with reactive hydrogen O tion, the organic solvent can be partially or even com atoms, which may be concurrently used, may for example pletely replaced by water. Those solutions which contain be the usual glycols, such as 1,4-butane diol, polyhydric about 80-100 percent of water in the solvent are also of alcohols such as trimethylol propane, diamines such as particular interest. ethylene diamine and amino alcohols such as ethanolamine By simply removing the solvent, a flexible, elastic plastic and the like. The quaternizable grouping can also be is obtained, which is substantially resistant to water but in present in the chain extender. To be mentioned as exam certain circumstances is soluble in acetone. This renders ples are the addition products of 2 mols of ethylene oxide possible in a simple manner more especially the produc or propylene oxide to monoalkylamines, such as methyl tion of foils and coatings and the use as adhesion pro diethanolamine, butyl diethanolamine, oley diethanol moters by casting the solution onto suitable supports and amine, N,N-dihydroxyethyl aniline, N,N-dihydroxyethyl removing the solvent while shaping. It may be expedient toluidine, alkyl diisopropanolamine, such as methyl diiso to effect the removal of the solvent at high temperatures, propanolamine, aryl diisopropanolamine such as phenyl advantageously at about 60 to 100° C. A treatment of the diisopropanolamine, dihydroxyethyl piperazine and the foils, coatings and adhesions after removing the solvent like. at high temperature, e.g. at about 80–140° C., leads to an The method preparing the aforesaid prepolymers is improvement in the strength and chemical resistivity. known. The components are brought together in any de According to one particular form of the process accord sired sequence.