EP0000722A1 - Process for the preparation of polyurethanes containing arylsulfonic acid alkyl ester groups - Google Patents

Abstract

The present invention relates to a process for the preparation of polyurethanes containing sulfonic acid ester groups, characterized by alkyl arylsulfonic acid groups bonded to aromatic cores as chain links.

Description

Linear polyurethane polysulfonic acid esters are known. For example, they can be prepared by using a sulfonic acid ester diol in the construction of a polyurethane. In DT-PS 1 156 977 and 1 184 946 it is proposed to implement, for example, polyether diols with diisocyanates and glycerol monotosylate in order to carry out a duating reaction from the polytethane polysulfonic acid esters obtained in this way, finally with mono- or difunctional tertiary amines, and so on To produce polyurethane ionomers. In these products, pendant aromatic sulfonic acid ester units are bound to an aliphatic chain segment. During the quaternization, the aromatic sulfonic acid residue is split off as an anion.

It is also known from US Pat. No. 3,826,769 to produce polyurethanes based on polyisocyanate sulfonic acids, polyurethane polysulfonic acids and their salts being obtained. For their preparation, either monomeric diisocyanates, for example tolylene diisocyanate, are sulfonated with sulfur trioxide and the sulfo obtained
niated diisocyanate used to build up a polyurethane or it. a prepolymer with terminal NCO groups is first prepared in the usual manner and this is sulfonated with sulfuric acid with simultaneous partial chain extension. The reaction products containing sulfonic acid groups are then neutralized with a base and mixed with water, resulting in aqueous polyurethane ionomer dispersions. Polyurethanes modified in this way by sulfonic acid groups or sulfonate groups often have considerable hydrophilicity, and the content of sulfonic acid groups should generally be kept as low as possible. In the manufacture of dispersions, e.g. B. Only introduce as much sulfonate groups as are absolutely necessary to achieve sufficient dispersion and to achieve a stable dispersion. A higher content of sulfonic acid groups would impair the water resistance of the coatings obtained from the dispersions. For this reason, the use of only 0.1-2%, based on the polyurethane, of sulfonating agents is recommended for the production of dispersions.

The production of highly filled polyurethanes or polyureas using polyisocyanate sulfonic acids is also known from DT-OS 2 359 611. Here, the sulfonic acid groups achieve special interactions between the organic binder and the fillers used, which results in high adhesive forces, even when very small amounts of binder are used. In the case of inorganic fillers, the sulfonic acid groups are generally neutralized directly on the particle surface. In this process too, in general I only use partially sulfonated polyisocyanates in order not to endanger the water and moisture resistance of the composites obtained.

The exclusive use of polyisocyanates in the form of their sulfonic acids would be of particular interest from a technical, toxicological and industrial hygiene point of view. Firstly, the sulfonic acids of aromatic isocyanates are solid, powdery substances that have no vapor pressure and are therefore particularly safe to process. On the other hand, when these isocyanates and the polyaddition products produced from them are broken down, water-soluble diaminosulphonic acids are formed which should not be toxic. With the exclusive use of isocyanate sulfonic acids for the construction of polyaddition products, however, highly hydrophilic, often even water-soluble products are obtained.

There is therefore a desire for a process which, on the one hand, permits the sole use of isocyanate sulfonic acids as the isocyanate component and, on the other hand, enables the production of hydrophobic water-resistant polyurethanes. A solution to this problem is the subject of the present invention. Surprisingly, it was found that the desired hydrophobic polyurethanes are obtained when aromatic polyisocyanate sulfonic acids are reacted with oxiranes or oxetanes, with the simultaneous formation of sulfonic acid ester groups. The new polymers obtained according to the invention are therefore polyurethane polysulfonic acid esters, which are characterized by arylsulfonic acid alkyl ester groups bonded to aromatic cores as chain links.

• 1. ermoglicht es eine günstige Kombination der Isocyanat-Chemie mit der Epoxyd- bzw. Oxetan-Chemie, wobei die Reaktion zwischen der Isocyanat-Komponente u. dem Epoxyd bzw. Oxetan ber Raumtemperatur u. in Abwesenheit von Katalysatoren stattfindet;
• ₂. wird ein neues Reaktionsprinzip vorgeschlagen, nach dem die Isocyanat-Komponente schon mit einem Mono-Epoxyd- bzw. Oxetan, aber auch mit Di- o. Polyepoxyden bzw. Oxetanen in einfacher Weise verlängert u. vernetzt werden kann. Die sich dabei abspielende Reaktion ist wahrscheinlich so zu erklären, daß sich in einem 1. Reaktionsschritt die Sulfonsäuregruppe an den Heterocyclus addiert u. die dabei gebildete OH-Gruppe im 2. Schritt mit einer Isocyanatgruppe zum Urethan umgesetzt wird,
• 3. ermöglicht das Verfahren den Aufbau von Polyurethanen unter alleiniger Verwendung von Polyisocyanatsulfonsäuren als Isocyanat-komponente, wobei hydrophobe, nicht wasserempfindliche Produkte erhalten werden;
• 4. ist das Verfahren unter Einbeziehung der üblichen bei der Urethan-Herstellung verwendeten Komponenten sehr vielseitig variierbar, wedurch sowohl harte Duromere als auch Elastomere aller Härtebereiche, homogen oder geschäumt, hergestellt werden können;
• 5. beim Abbau der erfindungsgemäßen Polyurethan-Polysulfonsäureester entstehen toxikologisch unbedenkliche Produkte.

The method according to the invention is advantageous in several aspects:

• 1. enables a favorable combination of the isocyanate chemistry with the epoxy or oxetane chemistry, the reaction between the isocyanate component u. the epoxy or oxetane above room temperature u. takes place in the absence of catalysts;
• _2nd A new reaction principle is proposed, according to which the isocyanate component is extended and expanded in a simple manner with a mono-epoxy or oxetane, but also with di- or polyepoxides or oxetanes. can be networked. The reaction taking place can probably be explained in such a way that in a first reaction step the sulfonic acid group is added to the heterocycle and u. the OH group formed in the second step is reacted with an isocyanate group to form urethane,
• 3. the method enables the construction of polyurethanes using only polyisocyanate sulfonic acids as the isocyanate component, hydrophobic, non-water-sensitive products being obtained;
• 4. the process can be varied in a wide variety of ways, including the usual components used in the production of urethane, by means of which both hard duromers and elastomers of all hardness ranges, homogeneous or foamed, can be produced;
• 5. When the polyurethane polysulfonic acid esters according to the invention are broken down, toxicologically harmless products are formed.

The present invention thus relates to polyurethanes containing sulfonic acid ester groups, characterized by alkyl arylsulfonic acid groups bonded to aromatic nuclei as chain links. These products preferably contain recurring units of the general formula

Ar = radical of an aromatic isocyanate, and in particular recurring units of the general formula

The new polyurethanes preferably have a molecular weight of over 12,000.

The present invention furthermore relates to a process for the preparation of arylsulfonic acid alkyl ester groups, characterized in that aromatic isocyanatosulfonic acids are reacted at 0-190 ° C. with oxiranes and / or oxetanes, the equivalent ratio of NCO groups to SO ₃ H groups. 0.1 to 1.99 (preferably 0.2-1) and the equivalent ratio of epoxy or oxetane groups to SO ₃ H groups is 0.2-5 (preferably 0.5-2). It is particularly preferred to use polyether and / or polyester polyols (customary in polyurethane chemistry) or to use aromatic isocyanate sulfonic acids which already contain polyethers and / or polyester units.

The preparation of spatially cross-linked polyurethane polysulfonic acid esters based on aromatic polyisocyanatosulfonic acids is particularly preferred.

According to the invention, the sulfonation products of all known aromatic di- or polyisocyanates can be used as isocyanates.

• 4,4'-Stilbendiisocyanat, 4,4'-Dibenzyldiisocyanat, 3,3'- bzw. 2,2'-Dimethyl-4,4'-diisocyanato-diphenylmethan, 2,5,2', 5'-Tetramethyl-4,4'-diisocyanato-diphenylmethan, 3,3'-Dimethoxy-4,4'-diisocyanato-diphenylmethan, 3,3'-Dichlor-4,4'-diisocyanatodiphenylmethan, 4,4'-Diisocyanato-dimethylmethan, 4,4'-Diisocyanato-diphenyl-cyclohexylmethan, 4,4'-Diisocyanato-benzophenon, 4,4'-Diisocyanato-diphenylsulfon, 4,4'-Diisocyanatodiphenyläther, 4,4'-Diisocyanato-3,3'-dibrom-diphenylmethan, 4,4'-Diisocyanato-3,3'-diäthyl-diphenylmethan, 4,4'-Diisocyanato-diphenyl-äthylen-(1,2), 4,4'-Diisocyanato-diphenyl-sulfid, 1,3- und 1,4-Phenylendiisocyanat, 2,4- und 2,6-Toluylendiisccyanat sowie beliebige Gemische dieser Isomeren, Diphenylciethan-2,4'- und/oder -4,4'-diisocyanat, Naphtylen-1,5-diisocyanat, Triphenylmethan-4,4'-4''-triiaocyanat, Polyphenyl-polymethylen-polyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung erhalten und z.B. in den britischen Patentschriften 874 430 und 848 671 beschrieben werden, Carbodiimidgruppen aufweisende Polyisocyanate, wie sie in der deutschen Patentschrift 1 092 007 beschrieben werden, Diisocyanate, wie sie in der amerikanischen Patentschrift 3 492 330 beschrieben werden, Allophanatgruppen aufweisende Polyisocyanate, wie sie z.B. in der britischen Patentschrift 994 890, der belgischen Patentschrift 761 626 und der veröffentlichten holländischen Patentanmeldung 7 102 524 beschrieben werden, Isocyanuratgruppen aufweisende Polyisocyanate, wie sie z.B. in den deutschen Patentschriften 1022 789, 1 222 067 und 1 027 394, sowie in den DT-OS 1 929 034 und 2 004 048 beschrieben werden, acylierte Harnstoffgruppen aufweisende Polyisocyanate gemäß der deutschen Patentschrift 1 230 778, Biuretgruppen aufweisende Polyisocyanate, wie sie z.B. in der Patentschrift 1 101 394, in der britischen Patentschrift 889 050 und in der französischen Patentschrift 7 017 514 beschrieben werden. Es ist auch möglich, die bei der technischen Isocyanatherstellung anfallenden Isocyanatgruppen aufweisenden Destillationsrückstände, gegebenenfalls gelöst in einem oder mehreren der vorgenannten Polyisocyanate, einzusetzen. Ferner ist es möglich, beliebige Mischungen der vorgenannten Polyisocyanate zu verwenden.

Examples of such isocyanates are:

• 4,4'-stilbene diisocyanate, 4,4'-dibenzyl diisocyanate, 3,3'- or 2,2'-dimethyl-4,4'-diisocyanatodiphenylmethane, 2,5,2 ', 5'-tetramethyl-4 , 4'-diisocyanato-diphenylmethane, 3,3'-dimethoxy-4,4'-diisocyanato-diphenylmethane, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-dimethylmethane, 4.4 '-Diisocyanato-diphenyl-cyclohexylmethane, 4,4'-diisocyanato-benzophenone, 4,4'-diisocyanato-diphenylsulfone, 4,4'-diisocyanatodiphenyl ether, 4,4'-diisocyanato-3,3'-dibromo-diphenylmethane, 4 , 4'-diisocyanato-3,3'-diethyl-diphenylmethane, 4,4'-diisocyanato-diphenyl-ethylene- (1,2), 4,4'-diisocyanato-diphenyl-sulfide, 1,3- and 1, 4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylciethan-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4, 4'-4 '' - triiaocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in the British patents 874 430 and 848 671, carbodiimide group-containing polyisocyanates, as described in German Patent 1,092,007, diisocyanates as described in American Patent 3,492,330, allophanate group-containing polyisocyanates, as described, for example, in British Patent 994 890, the Belgian patent specification 761 626 and the published Dutch patent application 7 102 524, polyisocyanates containing isocyanurate groups, as described, for example, in German patent specifications 1022 789, 1 222 067 and 1 027 394, and in DT-OS 1 929 034 and 2 004 048 are described, acylated urea group-containing polyisocyanates according to German Patent 1,230,778, biuret group-containing polyisocyanates as described, for example, in Patent Document 1,101,394, British Patent Specification 889,050 and French Patent Specification 7,017,514. It is also possible to use the distillation residues containing isocyanate groups obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.

Phosgenation products of condensates of aniline and aldehydes or are also suitable
Ketones, such as acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone, etc. Also suitable are the phosgenation products of condensates of anilines which are alkyl-substituted at the core, in particular toluidines with aldehydes or ketones, such as, for example, formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone, etc.

Reaction products of the aromatic polyisocyanate mixtures mentioned with 0.2-50 mol percent of polyols are also suitable, provided that the viscosity of the reaction products thus obtained does not exceed 50,000 cP at 25 ° C. and the NCO content of the reaction products is at least 6 Weight percent is. Suitable polyols for modifying the starting materials are in particular the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, and low molecular weight polyols of the molecular weight range 62 to 200 known in polyurethane chemistry. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, glycerol, trimethylolpropane, 1,4,6 -Hexanetriol etc.

Completely sulfonated isocyanates are preferably used which carry one to two sulfonic acid groups in the molecule. The mono- and disulfonic acids of 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, 2,4-diisocyanatotoluene, 2,4-diisocyanatotoluene and their mixtures of isomers are very particularly preferred.

However, it is of course also possible to use only partially sulfonated polyisocyanates, in particular partially sulfonated liquid mixtures of polyisocyanates, as described, for example, in DT-OS 2 227 111, 2 359 614 and 2 _. 359,615. Whole or partially sulfonated phosgenation products of aniline-formaldehyde condensates are particularly preferred.

The sulfonation products of aromatic monoisocyanates, e.g. of phenyl isocyanate, p-tolyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, p-methoxyphenyl isocyanate, m-chlorophenyl isocyanate, m-chloromethylphenyl isocyanate, p-chloromethylphenyl isocyanate.

_D a according to the invention both the isocyanate group and the sulfonic respond are those Monoisocyanatsulfon acids to be regarded as difunctional or polyfunctional compounds. The sulfonation of the isocyanates is carried out in a known manner, preferably using sulfur trioxide, oleum or sulfuric acid. The sulfonation can be carried out in a separate reaction step and the sulfonic acid isocyanates isolated from the sulfonation mixture and, if appropriate, dried and fed to the process according to the invention in this form. However, it is possible just as well sulfonic fonierun ^g in situ perform, which has the advantage that the moisture-sensitive Isocyanatsulfonsäuren do not need to be isolated.

Sulfonation in situ is particularly preferred when sulfonic acids of isocyanate prepolymers are used.

The sulfonation can be carried out in a known manner with sulfuric acid, oleum or sulfur trioxide and with organic compounds in which sulfur trioxide is additively bound, with the exclusion of water. The sulfur trioxide can be in liquid, dissolved or gaseous, e.g. form diluted by nitrogen. Suitable solvents are e.g. Tetrahydrofuran, aliphatic ether, dioxane, dimethylformamide, dichloroethane, chlorobenzene, tetrachloroethane, dichloroethane, methylene chloride, chloroform ,. Sulfur dioxide. Very particularly suitable solvents for the sulfonation component are products which can remain in the reaction mixture or in the finished product as plasticizers or as blowing agents, such as Chlorofluorocarbons, chloroethane, methylene chloride, triethyl phosphate, tris chloroethyl phosphate, tris dibromopropyl phosphate. (DT-OS 2 650 172) '

Powdered isocyanate sulfonic acids are often used in the form of wet powders, pastes or suspensions prepared with inert suspending agents (DT-OS 2 642 114). When in situ sulfonation is used, care must be taken to ensure that the sulfonation reaction is complete when the epoxy is mixed in.

In addition to the isocyanate sulfonic acids, it is of course also possible to use the polyisocyanates customary in polyurethane chemistry (up to 50% by weight, based on the isocyanate component), such as the polyisocyanates already mentioned above as the starting material for the sulfonation, furthermore aliphatic polyisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1, 3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DT-AS 1 202 785, US Pat. No. 3,401,190), 2, 4- and 2,6-hexanhydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate and their derivatives, e.g. Urethanes, biurets as mentioned in the above list among aromatic polyisocyanates.

Components which may also be used according to the invention are furthermore compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of generally 400-10,000. In addition to compounds containing amino groups, thiol groups or carboxyl groups, these are preferably polyhydroxyl compounds, in particular two to eight hydroxyl group-containing compounds, especially selche from molecular weight 800 to 10,000, preferably 1000 to 6000, for example at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl-containing polyesters, polyethers. Polythioethers, polyacetals, polycarbonates, polyesteramides, as are known per se for the production of homogeneous and cellular polyurethanes.

The polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated. Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, malefic acid, malefic acid, malefic acid, malefic acid, anhydride, maleic acid, malefic acid anhydride, maleic acid, malefic acid, fatty acid, malefic acid, fatty acid, malefic acid, anhydrous acid with monomeric fatty acids, dimethyl terephthalate, bis-glycol terephthalate. Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol Dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The polyesters can have a proportion of terminal carboxyl groups. Lactone polyesters, for example ε-caprolactone or hydroxycarboxylic acids, for example ω-hydroxycaproic acid, can also be used.

The at least two, generally two to eight, preferably two to three, hydroxyl-containing polyethers which are suitable according to the invention are also of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin with itself, e.g. in the presence of BF ₃ , or by attaching these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, e.g. water, ethylene glycol, propylene glycol (1,3) or - (1 , 2), trimethylol propane, 4,4'-di _h ydroxy- diphenylpropane, aniline, ammonia, ethanolamine, ethylene diamine prepared. Sucrose polyethers, such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups. Polyethers modified by vinyl polymers, such as those obtained by polymerizing styrene or acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1,152,536) are also suitable. likewise polybutadienes containing OH groups.

Among the polythioethers, the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular. Depending on the co-components, the products are polythio ether, polythio ether ester, polythlo ether amide.

As polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldiaethylmethane, hexanediol and formaldehyde. Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.

Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetreethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.

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

Also prepare urethane or urea group-containing poly-h ^y droxylverbindungen and optionally modified natural polyols such as castor oil, carbohydrates, starch, be used. Addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can also be used according to the invention.

According to the invention, however, polyhydroxyl compounds can also be used in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form. Modified polyhydroxyl compounds of this type are obtained if polyaddition reactions (for example reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (for example between formaldehyde and phenols and / or amines) are carried out directly in situ in the abovementioned hydroxyl groups Connections expire. Such methods are described, for example, in German Auslegeschrift 1 168 075 and 1 260 142, and German Offenlegungsschriften 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,550,796, 2,550,797, 2,550,833 and 2,550 862. However, it is also possible to mix a finished aqueous polymer dispersion with a polyhydroxyl compound in accordance with US Pat. No. 3,869,413 or German Offenlegungsschrift 2,550,860 and then remove the water from the mixture. i

Representatives of these compounds to be used according to the invention are e.g. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, Pages 5-6 and 198-199, as well as in the plastics manual, volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. described on pages 45 to 71.

Of course, mixtures of the abovementioned compounds with at least two hydrogen atoms which are reactive with isocyanates and have a molecular weight of 400-10,000, e.g. Mixtures of polyethers and polyesters can be used.

Compounds with at least two hydrogen atoms which are reactive towards isocyanates and have a molecular weight of 32-400 are also suitable as components to be used according to the invention. In this case too, this means hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups, preferably compounds having hydroxyl groups and / or amino groups, which serve as chain extenders or crosslinking agents. This ver As a rule, bonds have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms. Examples of such compounds are: ethylene glycol, (1,2) and - (1,3) propylene glycol, (1,4) and - (2,3) butylene glycol, (1,5) pentanediol, hexanediol (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols, 4,4'-diol, di-diol, up to 400 hydroxymethyl hydroquinone, ethanolamine, diethanolamine, triethanolamine, 3-aminopropanol, ethylenediamine, 1,3-diaminopropane, 1-mercapto-3-amino-propane, 4-hydroxy- or amino-phthalic acid, succinic acid, adipic acid, hydrazine, N, N'-dimethylhydrazine, 4,4'-diaminodiphenylmethane.

In this case too, mixtures of different compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-400 can be used.

• Äthylenoxyd, Propylenoxyd, Buten-1,2-oxyd, Buten-2,3-oxyd, 1,4-Dichlor-buten-2,3-oxyd, Styroloxyd, 1,1,1-Trichlorpropen-2,3-oxyd, 1,1,1-Trichlorbuten-3,4-oxyd, 1,4-Dibrombuten-2,3- oxyd, Epichlorhydrin, Epibromhydrin, Glycid, Glycerin-monoglycidyläther, Isobutenoxid, p-Glycidylstyrol, N-Glycidylcarbazol, Cyanäthylglycidyläther, Trichloräthylglycidyläther, Chloräthylglycidyläther, Bromäthylglycidyläther, Vinyloxiran, 3,4-Dichlorbuten-1,2-oxid, 2-(1-Chlorvinyl)-oxiran, 2-Chlor-2-vinyl-oxiran, 2,3-Epipropylphosphonsäurediäthylester, 3,4-Bis-hydroxy-buten-1,2-oxid, 2-Methyl-2-vinyl-oxiran, 2-(1-Methylvinyl-)oxiran.

Examples of suitable oxiranes and oxetanes according to the invention are: aliphatic, cycloaliphatic, aromatic or heterocyclic mono-, di- and polyepoxides; also epoxides which contain hydroxyl groups. Examples of monoepoxides are:

• Ethylene oxide, propylene oxide, butene-1,2-oxide, butene-2,3-oxide, 1,4-dichlorobutene-2,3-oxide, styrene oxide, 1,1,1-trichloropropene-2,3-oxide, 1,1,1-trichlorobutene-3,4-oxide, 1,4-dibromobutene-2,3- oxide, epichlorohydrin, epibromohydrin, glycid, glycerol monoglycidyl ether, isobutene oxide, p-glycidyl styrene, N-glycidyl carbazole, cyanoethyl glycidyl ether, trichloroethyl glycidyl ether, chloroethyl glycidyl ether, bromoethyl vinyl chloride, 1-chloroethyl dichloride, 1-chloroethyl-dichloride, 1-chloroethyl-dichloridyl ether, 1-chloroethyl-dichloride, 1-chloroethyl-dichloro-1-yl ) -oxirane, 2-chloro-2-vinyl-oxirane, 2,3-epipropylphosphonic acid diethyl ester, 3,4-bis-hydroxy-butene-1,2-oxide, 2-methyl-2-vinyl-oxirane, 2- (1 -Methylvinyl-) oxirane.

The products are also suitable for the epoxidation of natural fats and oils, such as soybean oil, olive oil, linseed oil, trans-oil, and of synthetic di- or polyesters which contain unsaturated fatty acids, such as oleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid.

Esters of glycid with monocarboxylic acids, e.g. Glycidyl acetate, glycidyl chloroacetate, glycidyl dichloroacetate, glycidyl trichloroacetate, glycidyl bromoacetate, glycidyl acrylate, glycidyl methacrylate, glycidyl caproate, glycidyl octoate, glycidyl dodecanoate, glycidyl ether, e.g. glycidyl oleate, glycidyl oleate, e.g. with phenol and substituted, especially halogenated phenols.

The reaction products of hydroxy-oxiranes, in particular of glycid with aliphatic, cycloaliphatic and aromatic mono- and polyisocyanates, are also very suitable.

To increase the crosslink density, it is also possible to use di- and polyepoxides, either alone or in combination with the monoepoxides listed above.

Such di- and polyfunctional epoxides are, for example, the epoxidation products of aliphatic and cycloaliphatic Diolefins, such as diepoxibutane, diepoxihexane, vinyl cyclohexene dioxide, dicyclopentadiene dioxide, limonene dioxide, dicyclopentadiene dioxide, ethylene glycol bis (3,4-epoxytetrahydro-dicyclopentadien-8-yl) ether, (3,4-epoxytetrahydrodadyl -glycidyl ether, epoxidized polybutadienes or copolymers of butadiene with ethylenically unsaturated compounds, such as styrene or vinyl acetate, compounds with two epoxy cyclohexyl radicals, such as diethylene glycol bis- (3,3-epoxycyclohexane carboxylate), bis-3,4- (epoxycyclohexyl) succinate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexane-carboxylate and 3,4-epoxyhexahydrobenzal-3', 4'-epoxycyclohexane-1 ', 1 '-dimethanol.

Other materials to be used according to the invention are polyglycidyl esters, such as those obtained by reacting a dicarboxylic acid or by reacting cyanuric acid with epichlorohydrin or dichlorohydrin in the presence of an alkali. Such polyesters can be derived from aliphatic dicarboxylic acids, such as succinic acid or adipic acid, and in particular from nromatic dicarboxylic acid, such as phthalic acid or terephthalic acid. Diglycidyl adipate, diglycidyl phthalot and triglycidyl isocyanur can be mentioned in this connection.

Polyglycidyl ethers, such as those obtained by etherifying a dihydric or polyhydric alcohol, a diphenol or a polyphenol with epichlorohydrin or didhlorohydrin in the presence of an alkali, are carefully used. These compounds can be derived from glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-fentanediol, 1,6-hexanediol, 2,4,6-eexanetrioc, glycerol and in particular from Diphenols or polyphenols, such as resorcinol, pyrocatechol, hydroquinone, phenolputhalein. Pherol-formaldohyd condensation products of the type of Novolaks, 1,4-di-hydroxynaphthalene, dihydroxy-1,5-naphthalene, bis (hydroxy-4-phenyl) methane, tetrahydroxyphenyl-1, 1,2,2-ethane, bis (hydroxy-4-phenyl) methylphenylmethane , the bis (hydroxy-4-phenyl) tolylmethane, dihydroxy-4,4'-diphenyl, Bi ₈ (hydroxy-4-phenyl) sulfone and in particular bis- (hydroxy-4-phenyl) 2,2-propane or the condensation products a phenolic with an aldehyde or a ketone. In the latter case, they are epoxy resins with two or more epoxy groups and possibly with free hydroxyl groups. Among them, the epoxy resins which are produced from polyphenols and are marketed under the trade name NOVOLAK resins and which are polycondensation products of a phenol with formol are particularly suitable. The epoxy resins obtained are represented by the following formula:

Also suitable are polyglycidyl ethers of diphenols, which have been obtained by esterifying 2 moles of the sodium salt of an aromatic oxycarboxylic acid with one mole of a dihaloalkane or dihalodialkyl ether (cf. GB-PS 1 017 612), from polyphenols, at least by the condensation of phenols and long-chain 2 halogen paraffins containing halogen atoms were obtained (cf. GB-PS 1 024 288). Further can be mentioned: polyepoxide compounds based on aromatic amines and E ^p ichlor- hydrin, for example, N-di- (2,3-epoxypropyl) -aniline, N, N'-dimethyl-N, N'-4,4-diepoxypropyl '-diamino-diphenylmethane, N, N'-tetra- epoxypropyl-4,4'-diaminodiphenylmethane, N-diepoxypropyl-4-aminophenylglycidether (see GB-PS 772 830 and 816 923). Also suitable are: glycidyl esters of polyvalent aromatic and cycloaliphatic carboxylic acids, for example phthalic acid diglycidyl with more than 5.5 epoxide equivalents per kg and glycidyl esters of reaction products from 1 mol of an aromatic or cycloaliphatic dicarboxylic acid anhydride and 1/2 mol of a diol or 1 / n moles of a polyol with n-hydroxyl groups or hexahydrophthalic acid diglycidyl esters, which may optionally be substituted by methyl groups.

Glycidyl compounds based on inorganic acids, such as e.g. Triglycidyl phosphate, glycidyl ether of hydroxyphenyl phosphoric acid ester, diglycidyl carbonate, tetraglycidyl titanate, furthermore epoxy alkyl phosphine oxides (DT-AS 1 943 712).

(= 3,4-Epoxicyclohcxylmethyl-3',4'-epoxicyclhexancarboxylat),

(= 3,4-Epoxi-6-methylcyclohexylmethyl-3',4'-epoxi-6'-methyl- cyclohexancarboxylat) und

(=3,4-Epoxihexahydrobenzal-3',4'-epoxicyclohexan-1',1'-di- methanol.Cycloaliphatic epoxy compounds are also suitable. For example, the compounds of the following formulas can be mentioned:

(= 3,4-Epoxicyclohcxylmethyl-3 ', 4'-epoxicyclhexanecarboxylate),

(= 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexane carboxylate) and

(= 3,4-epoxyhexahydrobenzal-3 ', 4'-epoxicyclohexane-1', 1'-di-methanol.

als auch das N,N'-Diglycidyl-dimethylhydantoin der folgenden Formel

Particularly suitable heterocyclic epoxy compounds are the triglycidyl isocyanurate of the following formula

as well as the N, N'-diglycidyl-dimethylhydantoin of the following formula

It further t i _ß possible to use mixtures of such cycloaliphatic and / oderheterocyclischer epoxy compounds.

worin z eine ganze oder gebrochene kleine Zahl im Bereich von O bis 2 bedeutet.Other preferred compounds are the polyglicydyl ethers of bis (p-hydroxyoxyphenyl) dimethyl methane (bis-phenol A), which correspond to the following average formula:

where z is an integer or fractional small number in the range of 0 to 2.

Other suitable diepoxides are, for example: glycerol diglycidyl ether, diglycidyl N, N 'ethylene urea, diglycidyl N, N' propylene urea, N, N 'diglycidyl urea, N, N' diglycidyl dimethyl urea, and oligomers of these compounds, di-, tri- or tetraglycidyl-acetylene diurea, and oligomers of these compounds. Further epoxides which are used according to the invention can be found, for example, in Houben-Weyl, edited by Eugen Müller, 1963, volume XIV / 2, pages 462-538.

Examples of suitable monooxetanes are; Trimethylene oxide, 3,3-dimethyloxetane, 3,3-diethyloxetane, 3,3-dipropyloxetane, 3,3-dibutyl-oxetane, 3-methyl-3-dodceyl-oxetane, 3-ethyl-3-stearyl-oxetane, 3, 3-tetramethylene-oxetane, 3,3-pentamethyleneoxetane, 2,6-dioxaspiro (3,3) -heptane, 3-methyl-3-phenoxymethyl-oxetane, 3-ethyl-3-phenoxymethyl-oxetane, 3-methyl-3 -chlorine methyl-exetane, 3-ethyl-e-chloromethyl-oxetane, 3-butyl-3-chloromethyl-oxetane, 3-dodecyl-3-chloromethyl-oxetane, 3-stearyl-3-chloromethyl-oxetane, 3-methyl-3- trommethyl-oxetane, 3-atnyl-3-trommethyl-oxetane, 3-propyl-3-bromomethyl-oxetane, 3-dodecyl-3-trommethyl-oxetane, 3,3-bis-chloromethyl-oxetane, 3,3-bis bromethyl-oxetane, 3-methyl-3-hydroxymethyl-oxetane, 3-ethyl-3-hydroxymethyl-oxetane, 3-amyl-3-hydroxymethyl-oxetane, 3,3-bis-hydroxymethyl-oxetane, as well as ethers, esters, urethanes these hydroxy-oxetanes, such as 3-ethyl-3-methoxymethyl-oxetane, 3-ethyl-3-butoxymethyl-oxetane, 3-ethyl-3-dodecycloxymethyl-oxetane, 3-ethyl-3-acetoxymethyl-oxetane, 3-ethyl -3-stearoyloxy-cxetane, 3-ethyl-3-N-methyl-carbamoylmethyl-oxetane, 3-ethyl-3-N-chloroethyl-carbomoylmethyl-oxotane, 3-ethyl-3-N-poenylearbomoylmethyl-oxetane, 3- Ethyl-3-N-dichlorophenyl-cartamoylmethyl-oxetane, 3-ethyl-3-N-stearylcarbamoylmethyl-oxetane, 3,3-bis-phenoxymethyl-oxetane, 3,3-bis- (4-chlorophenoxymethyl) -oxetane, 3,3-bis (2,4-dichlorophenoxymethyl) cxet an, 3,3-bis-carbamoylmethyl) -oxetane, 3-phenoxymethyl-3-carbamoylmethyl-oxetane. Further suitable oxetanes can be found, for example, in German Auslegeschrift 1,668,900, columns 3 and 4.

Of course, the oxetane analogs of the glycid derivatives listed above can also be used, e.g. 3-ethyl-3-acryloxy-oxetane, 3-ethyl-3-methacryloxy-oxetane, 3-methyl-3-trichloroacetoxy-oxetane, 3-methyl-3-β-cyanoethoxymethyl-oxetane, 3-ethyl-ß-cyanoethoxymethyl oxetane, 3-ethyl-3-phenoxymethyl-oxetane.

Among the di- and polyoxetanes which can be used according to the invention, the reaction products of 3-alkyl-3-hydroxymethyl-oxetanes with di- and polycarboxylic acids, and with di- and polyisocyanates are of particular importance. The di- and polyethers of the hydroxy-oxetanes derived from aliphatic, cycloaliphatic and aromatic diols and polyols are also very suitable, furthermore bis-oxetanyl esters (DT-AS 1 907 117),

likewise phosphoric acid esters and phosphoric acid esters, such as tris (3-methyloxetanylmethyl) phosphite, tris (3-ethyloxetanylmethyl) phosphite, tris (3-ethyloxetanylmethyl) phosphate.

Hydrophobic, water-insoluble, and liquid mono- and polyepoxides, such as, for. B. polyglycidyl ether of polyhydric phenols, especially from bisphenol A; Polyepoxide compounds based on aromatic amines, in particular bis (N-epoxypropyl) aniline, N. N '-dimethyl-N, N' -diepoxypropyl-4, 4 '-diamino-diphenylmethane and N-diepoxypropyl-4-amino- phenylglycidyl ether; Polyglycidyl esters of aromatic or cycloaliphatic dicarboxylic acids, especially hexahydrophthalic acid diglycidyl ester or phthalic acid diglycidyl ester with more than 5.5 epoxy equivalents / kg, and phosphoric acid triglycidyl ester, 3-ethyl-3-hydroxymethyloxetane and the like. its esters, ethers and urethanes. Glycid, epichlorohydrin, trichlorobutene oxide.

These products are particularly easy to process in the context of polyurethane technology and provide polyurethane polysulfonic acid esters with particularly good water and moisture resistance.

• Tertiäre Amine, wie Triäthylamin, Tributylamin, N-Methylmorpholin, N-Äthyl-morpholin, N-Cocomorpholin, N,N,N',N'-Tetramethyläthylen-diamin, 1,4-Diaza-bicyclo-(2,2,2)-octan, N-Methyl-N'-dimethylamino-äthyl-piperazin, N,N-Dimethylbenzylamin, Bis-(N,N-diäthylaminoäthyl)-adipat, N,N-Diäthylbenzyl- amin, Pentamethyldiäthylentriamin, N,N-Di-methylcyclohexyl- amin, N,N,N',N'-Tetramethyl-1,3-butandiamin, N,N-Dimethyl- ß-phenyläthylamin, 1,2-Dimethylimidazol, 2-Methylimidazol.

When carrying out the reaction between isocyanatosulfonic acid and oxirane or oxetane, no catalysts are generally required, since the sulfonic acid group generally attaches to the oxirane ring or oxetane ring at room temperature with sufficient speed. However, it may be expedient to catalyze the addition of the hydroxyl groups formed with the isocyanate group. For this purpose, the usual catalysts common in polyurethane chemistry can be used, for example:

• Tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N, N, N ', N'-tetramethylethylenediamine, 1,4-diaza-bicyclo- (2,2,2 ) octane, N-methyl-N'-dimethylamino-ethyl-piperazine, N, N-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-di -methylcyclohexyl amine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole.

Tertiary amines which have hydrogen atoms active against isocyanate groups are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.

Silaamines with carbon-silicon bonds, such as those e.g. described in DT-PS 1 229 290, in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane.

Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines, 2,4,6-tris (dimethylaminomethyl) phenol, aluminum alcoholates and triphenylphosphine can also be used as catalysts.

According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts.

Preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acetate. Tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin salts of carboxylic acids such as e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin naleate or dioctyltin diacetate.

Further representatives of catalysts to be used according to the invention and details of the mode of action of the catalysts are in the plastics manual, volume VII, published by Vieweg and Höchtlen, CarlrHanser-Verlag, Munich 1966, e.g. B. described on pages 96 to 102.

The catalysts are generally used in an amount between about 0.001 and 10% by weight, based on component a).

Tert are particularly preferred. Low alkylation amines, as well as organometallic compounds. In any case, care should be taken to ensure that the catalysts are not alkylated too early by the sulfonic acid ester groups and thus become ineffective. On the other hand, such "destruction" of the catalyst at the end of the reaction may be desirable and contributes to the stability of the reaction product. Of course, in addition to di- or polyepoxides, undershot amounts of conventional epoxy hardeners can also be used, for example amines which contain at least 2 hydrogen atoms which are bonded directly to the nitrogen, for example aliphatic and aromatic, primary and secondary amines such as mono- and dibutylamine, p -Phenylenediamine, bis-p-aminophenyl) methane, ethylenediamine, N, N-diethyl-ethylenediamine, diethylenetriamine, tetra- (hydroxyethyl) -diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, guanidine and guanidineamine, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandididine derivatives, such as phenylgandidinamine, Polymers of aminostyrenes and polyaminoamides, such as those made from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids, polyhydric phenols such as resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, phenyl aldehyde resins and oil-modified phenol Aldehyde resins, reaction products from n Aluminum alcoholates or phenates with tautomer reacting compounds of the Acetoessigsäureesterart, Friedel-Crafts catalysts, such as AlCl _3, SnCl _4, ZnCl _2, BF ₃ and its complexes with organic compounds, phosphoric acid and polycarboxylic acids and their anhydrides, for example phthalic anhydride, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, Hexachlorendomethylentetrahydrophthalsäureanhydride or _E ndeomethylentetrahydrophthalsäureanhydride or their mixtures or maleic or succinic anhydrides.

According to the invention, surface-active additives (emulators and foam stabilizers) can also be used. As emulsifiers come .t z. B. the sodium salts of castor oil sulfonates or of fatty acids or salts of fatty acids with amines v ie oleic acid diethylamine or stearic acid diethanolamine in question. Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethane disulfonic acid or also of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.

In particular, water-soluble polyether siloxanes are used as foam stabilizers. These compounds are generally designed so that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane residue. Such foam stabilizers are such. Described in U.S. Patent 2,764,565. These additives are preferably used at 0.20% by weight, based on the reaction mixture.

The practical implementation of the method based on the starting materials mentioned is very simple and different do not differ from the procedures customary in polyurethane chemistry and known to the person skilled in the art. With regard to the practical implementation of the process, the epoxide or oxetane can be regarded as a polyol component, as it reacts bifunctionally as a monoepoxide with an isocyanate sulfonic acid.

In the simplest case, the isocyanatosulfonic acid is mixed with the epoxy or oxetane, whereupon the polyaddition takes place at room temperature and a polymer is formed. This procedure is particularly suitable when sulfonated liquid polyisocyanates or liquid NCO prepolymers are used. To produce foams, additional catalysts and blowing agents are added to the reaction mixture, and water can also be used to initiate the foaming reaction.

If solid, powdered isocyanate sulfonic acids are used, it must be ensured that the reaction mixture becomes homogeneous during the reaction, i.e. that the isocyanatosulfonic acid dissolves during the reaction. If this is not the case, work must be carried out in the presence of water or polar solvents or at elevated temperature. In a preferred embodiment of the process, the isocyanatosulfonic acid is first reacted with a polyol, in particular one of the polyether or polyester components customary in PU chemistry, with stirring and, if appropriate, external heat, to give a prepolymer having completely or largely homogeneous NCO groups and only then the epoxy or oxetane added.

According to another, likewise preferred procedure, the solid polyisocyanatosulfonic acid, which can be dispersed in conventional polyisocyanates, is mixed with the mixture of polyhydroxy compounds and epoxide or oxetane to form a dispersion mixes. As soon as the reaction starts, the sulfonic acid goes into solution.

The quantity ratios between the reaction components can be varied within wide limits, but it must always be taken into account that a high molecular weight poly. urethane should arise, which is essentially free of NCO groups. To calculate the NCO group equivalents relevant to the invention, first of all the equivalents of all zerewitinoff-active co-reactants, including the OH groups, which may be introduced into the reaction by hydroxyoxiranes or hydroxioxetanes, must be subtracted from the NCO group equivalents used in the form of the isocyanates be introduced. What is important is the content of NCO groups in the prepolymer formally formed from the sum of all isocyanates and the sum of all Zerewitinoff-active co-reactants (mostly polyols), regardless of whether such a prepolymer is actually wholly or partially in a first reaction step or whether the reaction with the epoxy component is carried out in a one-shot process.

The equivalent ratio of the NCC groups calculated in this way to the SO ₃ H groups should be between 0.1 and 1.99. However, this ratio is preferably 0.2-1. The lower area is realized when practically only isocyanatosulfonic acids are used and polyhydroxy compounds are also used. The upper area is realized either when working in the absence of additional polyols or other Zerewitinoffactive compounds, or when conventional non-sulfonated isocyanates are used to a greater extent and an approximately equivalent amount of polyols is used. If the NCO / SO ₃ H ratio is above 1, the use of zerewitinoff-active compounds in the formulation is mandatory, to the extent that the ratio exceeds 1. A ratio of 1.8 therefore requires at least 0.8 equivalents of polyol or the like.

To calculate the epoxy group equivalents relevant to the invention, the equivalents of any epoxy hardener that may be used must first be subtracted in an analogous manner. Primary and secondary amines generally react faster with the isocyanate group than with the epoxy group, so they can only be counted as epoxy hardeners if they are either added separately to the epoxy component for modification from the outset, or if they are added after the NCO groups have reacted Reaction approach are added at the end.

The equivalent ratio of epoxy groups to SO ₃ H groups should be 0.2-5, preferably 0.5-2. This means that, in extreme cases, only 20% of the total sulfonic acid groups present are esterified, for example if an ionic product carrying sulfonate groups is desired and the reaction with the epoxide is only intended to provide partial hydrophobization or to increase the degree of branching. On the other hand, the epoxy component can of course be used in excess, for example to ensure quantitative esterification, in order to introduce free epoxy groups into the polymer (for example to achieve optimal adhesion in coating materials or to have free epoxies as plasticizers or adhesion promoters in the polymer). Finally, it may also be desirable to carry out a reaction of free epoxy groups with free isocyanate groups or a trimerization following the reduction according to the invention as a heat curing step for the final crosslinking. With an NCO / SO ₃ H ratio above 1, an epoxy / SO ₃ H ratio above 1 is also preferably selected.

The reaction can be carried out in the presence or absence of solvents. If the presence of solvents does not interfere, it is expedient to first convert the isocyanate and the polyol components to a higher molecular weight prepolymer which, for example, has an average molecular weight of 5,000 to 20,000 and can be dissolved in one or more solvents. To make a coating
then the epoxy component, which can also be dissolved in a solvent, is combined with the solution of the prepolymer, the solution is applied and the solvent is removed by evaporation. At the same time or subsequently, the implementation according to the invention takes place on the substrate. Suitable solvents are e.g. B. ketones, esters, halogenated hydrocarbons, optionally in a mixture with hydrocarbons, dimethylformamide. The reaction is preferably carried out in the absence of customary solvents or in the presence of very small amounts of apolar solvents with which the isocyanate sulfonic acid is stabilized or in the presence of liquid plasticizers. The process is particularly suitable for the technologies of casting, reaction injection molding (RIM technology) and for the production of foam materials.

Various embodiments of the method according to the invention are of particular importance for the production of foams or microcellular materials and molded parts: For example, partially sulfonated liquid polyisocyanates can be used, such as sulfonated phosgenation products of aniline-formaldehyde condensation. The polyisocyanate is then homogeneously liquid and can be processed as usual.

Dispersions of solid sulfonated polyisocyanates in non-sulfonated liquid polyisocyanates can also be used, such as are obtained, for example, in the partial sulfonation of tolylene diisocyanate. If such dispersions are stable to sedimentation, for example after the dispersed phase has been comminuted in a milling device, they can be handled like liquid polyisocyanates. Dispersions that are not stable to sedimentation can, for example, be brought into solution by addition of an epoxide or oxetane under reaction immediately before foaming and then foamed with the polyhydroxy component the. However, the dispersion can also be reacted directly with polyol and epoxy or oxetane and the customary additional components with foaming in the one-shot process.

If only polyisocyanate sulfonic acids are used as the polyisocyanate component, these can be added to the reaction mixture in dry form, for example like fillers. It is cheaper to paste the solid polyisocyanate with the liquid polyol component and then to react it with blowing agent and epoxy. You can also dissolve the polyisocyanate in the epoxy component under reaction and then mix with the other components.

Compared to other known reactions between polyisocyanates and polyepoxides, it should be emphasized that the reaction according to the invention takes place at 0-30 ° C., in particular at room temperature. Heating the reaction mixture leads to a rapid acceleration of the reaction and is therefore only necessary if rapid reaction is desired. Of course it is possible, but not necessary, to work at temperatures above 80 ° C up to about 190 ° C. The preferred temperature range is 20-60 ° C, with the temperature increasing by about 10-80 ° C during the reaction.

Polar hydroxy compounds, such as polyethers and polyesters, which contain oxyethylene units, are particularly suitable as reactants for solid sulfonated polyisocyanates. Particularly suitable oxiranes or oxetanes are those which additionally contain free hydroxyl groups, such as glycid and 3-alkyl-3-hydroxymethyl-oxetane. A very particularly preferred embodiment of the process according to the invention consists of a monosulfonated diisocyanate, such as sulfonated tolylene to implement diisocyanate or sulfonated diisocyahatodiphenylmethane with approximately the equivalent amount of glycid or 3-ethyl-3-hydroxymethyl-oxetane and to add an approximately equivalent amount of conventional polyisocyanates for additionally used polyhydroxy compounds.

Because of the good adhesion of the polymers according to the invention to a wide variety of surfaces, in particular polar surfaces, the use of inorganic fillers is often advantageous. Preferred fillers are chalk, talc, dolomite, gypsum, clay, anhydrite, quartz powder, aluminum oxide hydrate, calcium aluminum silicates, cement, glass in the form of fiber, powder or beads. Other inorganic and organic fillers can e.g. can be found in DT-OS 2 359 609.

The usual blowing agents such as hydrocarbons, halogenated hydrocarbons are also used to produce foams. However, it can also be done using carbon dioxide (e.g. by using water in the formulation) or by means of dissolved gases, e.g. Compressed air can be foamed.

The process products are used in the usual fields of application known for compact or cellular elastomers, flexible foams, semi-rigid foams and rigid foams, in particular when high demands are placed on crosslinking density, fire behavior or degradability. The products obtainable by the process of the invention are suitable, for example, for the production of upholstery materials, mattresses, elastic underlays, car seats, damping materials, shock absorbers, construction materials, soundproof insulation, moisture-absorbing materials, e.g. in the hygiene sector, as substrates for plant breeding and for heat and cold protection.

• A) Herstellung von Präpolymeren mit endständigen NCO-Gruppen
  • I: 700 g (0, 35 Mol) eines auf Propylenglykol(1, 2) gestarteten Polypropylenätherglykols der OH-Zahl 56 werden mit 150 g (0,455 Mol) toluolfeuchtem Uretdion der Diisocyanatotoluolsulfonsäure (hergestellt aus Toluylendiisocyanat, Isomerengemisch 2, 4 : 2, 6 = 80 : 20) , entsprechend 15, 5 g Trockensubstanz bei Raumtemperatur innig vermischt.
    Die Suspension wird 12 Stunden gerührt, wobei die Temperatur von 25°C auf 41°C ansteigt und der größte Teil des Isocyanats unter Reaktion in Lösung geht. Nach 4 Stunden Rühren bei 70-76°C ist ein klares viskoses NCO-Präpolymer entstanden. Nach Zusatz von 85 g Tris-chloräthylphosphat beträgt die Viskosität bei Raumtemperatur 65 ooo cP. 89 g des Produkts enthalten 0, 02 Val NCO und 0, 043 ValSO₃H.
  • II:E wird wie unter I. verfahren, jedoch unter Verwendung von 500 g des dort beschriebenen Polyäthers, 165 g (entsprechend 127 g Trockensubstanz) des Uretdions der Diisocyanatotoluolsulfor.säure (Molverhältnis 1 : 2) und 66, 5 Tris-chloräthylphosphat. Viskosität bei Raumtemperatur: 40 000 cP. 58 g des Produkt enthalten 0,04 Val NCO und 0, 04 Val SO₃H.
  • III:132 g (0,05 Mol) eines Adipinsäure-Diäthylenglykol-Polyesters mit endständigen OH-Gruppen werden mit 100 g (0, 3 Mol) toluolfeuchtem Uretdion der Düsocyanatotoluolsulfonsäure, entsprechend 76 g Trockensubstanz bei 60°C vermischt. Innerhalb von 12 Stunden wird das Gemisch unter Rühren langsam bis 95°C erwärmt, wobei ein zähviskoses estermodifiziertes Diisocyanat gebildet wird.

Examples:

• A) Preparation of prepolymers with terminal NCO groups
  • I: 700 g (0.35 mol) of a polypropylene ether glycol started on propylene glycol (1, 2) with OH number 56 are mixed with 150 g (0.455 mol) of toluene-moist uretdione of diisocyanatotoluenesulfonic acid (prepared from tolylene diisocyanate, isomer mixture 2, 4: 2, 6 = 80:20), corresponding to 15.5 g of dry substance, intimately mixed at room temperature.
    The suspension is stirred for 12 hours, the temperature rising from 25 ° C. to 41 ° C. and most of the isocyanate dissolving under reaction. After 4 hours of stirring at 70-76 ° C, a clear, viscous NCO prepolymer was formed. After adding 85 g of tris-chloroethylphosphate, the viscosity at room temperature is 65,000 cP. 89 g of the product contain 0.02 Val NCO and 0.043 ValSO ₃ H.
  • II: E is carried out as under I., but using 500 g of the polyether described there, 165 g (corresponding to 127 g of dry substance) of the uretdione of diisocyanatotoluenesulfonic acid (molar ratio 1: 2) and 66.5 tris-chloroethylphosphate. Viscosity at room temperature: 40,000 cP. 58 g of the product contain 0.04 Val NCO and 0.04 Val SO ₃ H.
  • III: 132 g (0.05 mol) of an adipic acid-diethylene glycol polyester with terminal OH groups are mixed with 100 g (0.3 mol) of toluene-moist uretdione of diisocyanate-toluenesulfonic acid, corresponding to 76 g of dry matter at 60 ° C. The mixture is slowly heated to 95 ° C. with stirring in the course of 12 hours, a viscous ester-modified diisocyanate being formed.

Example 1:

89 g I and 6.8 g of the bis-glycidyl ether of bisphenol A are intimately mixed very quickly at 30 ° C. in a siliconized sheet metal dish, the viscosity increasing sharply. After 5 minutes, a clear, cross-linked elastomer has formed, which initially still has a certain plasticity. After 2 hours the surface is dry and the product can no longer be pressed in.

Example 2:

89 g of I and 2.9 g of 1,2-butene oxide are mixed. After 24 hours, 0.5 g of triethylamine are added to the viscous mass. You get a spatula product that z. B. can be used as a grout or sealant. In the course of a few weeks, a very weakly cross-linked elastic, but still plastically compressible mass is obtained.

Example 3:

89 g of I and 4. g of 3-ethyl-3-hydroxymethyloxetane are mixed. The viscosity increases very sharply within 24 hours, but the mass remains plastic. Reheating at 50-100 ° C leads to a very soft, sticky, plastically deformable elastomer.

Example 4:

89 g I and 40, 8 g of a 50 percent. Solution of the bis-glycidyl ether of bisphenol A in tris-chloroethyl phosphate are mixed at room temperature. In contrast to Example 1, the mixture is still flowing after 15 minutes. An hour later, a cross-linked elastomer was created.

Example 5:

The procedure is as in Example 4, but using 27.2 2 g of the 50 percent. Epoxy solution. The elastomer is significantly harder and more cross-linked than that obtained in Example 4.

Example 6:

58 g II and 6.8 g of the bis-glycidyl ether of bisphenol A are mixed at room temperature. After 10 minutes there is still a flowable mixture; after 30 minutes an elastomer is formed that initially still has a certain plasticity. After 6 hours the product is no longer deformable.

A sample of the elastomer is kept under water for 3 months. Small parts dissolve in water; the elastomer remains almost unchanged. The swelling is slight, no degradation was observed.

Example 7:

Example 3 is repeated, however, using 58 g II instead of I. A very soft, hardly tacky, crosslinked elastomer is obtained.

Example 8:

The procedure is as in Example 4, but using 58 g of II instead of I. After 1 hour, the mixture is still flowable. After 24 hours, a very soft, clear elastomer developed.

Example 9:

30 g III are stirred at 90 ° C. with a mixture of 3 g of the bis-glycidyl ether of bisphenol A and 2 g of epichlorohydrin. A hard cross-linked elastomer is created within a minute.

Example 10:

30 g III are stirred at 80 ° C with 3.6 g epichlorohydrin. A plastic mass is created within 48 hours that can be used as a putty and sealant.

Example 11.

• Component A: 100 g (0.05 mol.) Of a linear polyathers of molecular weight 2000 started on propylene glycol and containing 80% propylene oxide and finally 20% ethylene oxide are 11.6 g (0.1 mol) 3-hydroximethyl-3- mixed ethyl-oxetane. and added 2g Dabco 33LV as catalyst.
• Component 8: 25.4 g (0.1 mol) of uretdione or diisocyanatotoluenesulfonic acid (prepared from tolylene diisocyanate, mixture of isomers 2.4: 2.6 = 80:20), 8.7 g (0.05 mol) of tolylene diisocyanate and 4 g of toluene are mixed to form a paste.

Component A, heated to 606, is intimately mixed with component B. The tsocyanatosulfonic acid increasingly dissolves in the liquid mixture. After 15 minutes the mixture stopped flowing. After a few hours at room temperature, a slightly cloudy, completely tack-free elastomer is formed.

The hardening rate can be greatly accelerated if the mixture is reheated at 100 °.

In order to obtain a completely transparent elastomer, it is advantageous to reduce the isocyanato sulfonic acid to a particle size of max. 100 microns to grind and a small amount (3-10 g) _T riäthylphosphat add the component B.

Using a polyether with a higher content of ethylene oxide also leads to an acceleration of the reaction.

Example 12

The procedure is as in Example 11, but using 7.2 g (0.1 mol) of glycide instead of the oxetane. The elastomer obtained corresponds to that obtained in Example 11.

Example 13

• Component A: as in Example 11, but 0.2 g of tin dioctoate as catalyst instead of Dabco 33bV.
• Component B: as in Example 11.

The two components are mixed intimately at room temperature. The temperature rises to 380 ° C. After 60 minutes the mixture stops flowing. The elastomer obtained is somewhat softer than that obtained according to Example 11 and slightly sticky.

Example 14

Component B according to Example 11 is first mixed intimately with the polyether described in Example 11, component A, a white paste being formed with gentle heating. This is mixed with 11.6 g of 3-hydroxymethyl-3-ethyloxetane and 2 g of dimethylbenzylamine. The mixture is baked at 160 ° C. for 30 minutes. A transparent, tack-free elastomer is obtained.

Example 15

• Component A: 184.5 g (0.3 mol) of a linear polyethylene glycol polyether with a molecular weight of 615 are mixed with 29 g (0.25 mol) of 3-hydroximethyl-3-ethyloxetane.
• Component B: 63.5 g (0.25 mol) uretdione of diisocyanatotoluenesulfonic acid, 52.2 g (0.3 mol) tolylene diisocyanate and 20 g toluene are mixed to form a suspension.

Component A is heated to 40 ° C and mixed with component B. The temperature rises quickly to 85 ° C and a clear mixture is created. 8 minutes after the components had been combined, the polyaddition had progressed to such an extent that the mixture had become highly viscous. A cross-linked polyurethane is formed after 15 minutes. The thermoset formed is hard, tough and clearly transparent.

Water storage causes reversible softening, but there is only slight swelling and no hydrolytic degradation.

Example 16.

• Component A as in Example 15
• Component B: as in Example 15, but only 34.8 g (0.02 mol) of toluenediisocyanate.

Component A is heated to 60 ° and mixed quickly with component B. The temperature rises rapidly to 100 °, the isowyanato sulfonic acid dissolving. 3 minutes after combining the components, the mixture has solidified. The thermoset formed is softer and somewhat more elastic than that obtained in Example 15.

Example 17.

• Component A: 60.2 g (0.1 mol) of a linear polyether with a molecular weight of 602, which contains 50% propylene oxide and 50% ethylene oxide as structural components, with 23.2 g (0.2 mol) 3-hydroxy mixed methyl-3-thyl-oxetane.
• Component B: 50.8 g (0.2 mol) of _U retdion Diisocyanatotoluolsulfonsäure, 17.4 g (0.1 mol) of tolylene diisocyanate and 18 g of toluene are mixed to a paste.

The two components are mixed at 50 ° C. The solidification begins after 2 minutes. A very hard, but not brittle, colorless, only slightly cloudy duromer is obtained.

Example 18

Component A is heated to 50 ° C and quickly mixed with component B. The reaction mixture is foamed while the temperature rises rapidly to 117 ° C. An elastic, fine-pored foam is obtained.

Claims (7)

1. Polyurethanes containing sulfonic acid ester groups, characterized by alkyl arylsulfonic acid groups bonded to aromatic cores as chain links. 2. Polyurethanes containing sulfonic acid ester groups according to claim 1 with a molecular weight of more than 12,000. 3. Polyurethanes having sulfonic acid ester groups according to claim 1 and 2, which additionally contain polyether and / or polyester units. 4. A process for the preparation of arylsulfonic acid alkyl ester groups containing polyurethanes, characterized in that aromatic isocyanatosulfonic acids are reacted at 0-190 ° C with oxiranes and / or oxetanes, the equivalent ratio of NCO groups to S0 ₃ H groups 0.1 to 1.99 and the equivalent ratio of epoxy (or oxetane) groups to S0 ₃ H groups is 0.2 to 5. 5. The method according to claim 4, characterized in that the equivalent ratio of NCO groups to S0 ₃ H groups is 0.2-1 and the equivalent ratio of epoxy groups to S0 ₃ H groups is 0.5-2. 6. The method according to claim 4 and 5, characterized in that the aromatic isocyanato sulfonic acids contain polyether and / or polyester units. 7. The method according to claims 4-6, characterized in that the reaction is carried out in the presence of polyether and / or polyester polyols.