DE1595602A1 - Process for the production of polyurethane plastics - Google Patents

Description

Method of making polyurethane plastics It is made from DAS 1 184 946 known, plastics according to the diisocyanate polyaddition process thereby produce that one predominantly linear reaction products of polyhydroxyl compounds and polyisocyanates and optionally chain extenders, where at least one of the components at least a) a tertiary nitrogen atom, b) a halogen atom or c) contains an R-SO2-0 group, in solution with in case a) a monofunctional one Alkylating agent or in case b) or c) a tertiary amine and then reacted the solvent removed with shaping.

Furthermore, from DAS 1,178,586 and 1,179,363, basic, tertiary ones are known Polyurethanes containing N atoms in organic or aqueous solution with mono- or to treat polyfunctional acids. Obtained after removal of the solvent elastic polyurethane plastics are also used.

These plastics generally have a content of 0.2-2 % of quaternary ammonium nitrogen, which makes them non-ionic Polyurethanes obtained increased tensile strength, ductility, toughness, elasticity and hardness.

Depending on which polyhydroxyl compounds, polyisocyanates, chain extenders and alkylating agents or acids are used in the individual case and what proportions is chosen, you get polyurethane plastics with a wide variety of properties.

Soft, rubber or rubber-elastic adhesives can be used Products of various hardnesses, flexible thermoplastic products and products behave with the hardness of polystyrene or acrylic glass, whereby the products in each case distinguished by their special toughness. Also the lyophilicity and hydrophilicity the products can be controlled as desired within wide limits.

In addition, according to the teaching of the Belgian patent specification 653 223 and the aforementioned German Auslegeschriften such ionic polyurethanes without the aid of emulsifiers or other surface-active agents in simple Transfer way into an aqueous medium.

A quaternary content of 0.02% is required for dispersibility Ammonium nitrogen is sufficient. Favor even lower proportions of salt groups at least the emulsification of polyurethanes or pre-adducts containing isocyanate groups and thus make it possible to reduce the amount of emulsifier required.

Polyurethane compounds with a higher content of salt groups deliver extremely finely divided dispersions with particle diameters between 100 and 30 and finally optically almost clear colloidal solutions of associations, which, however, also become water-insoluble Dry flat structures. Real aqueous solutions with molecularly disperse distribution of the polyurethane macromolecules, as they are with a content of quaternary ammonium nitrogen of about 3 - 6% arise, have been known for a very long time, but technically from of minor interest, since their hydrophilicity is too great for many purposes.

These polyurethane plastics are preferably made from aqueous dispersions or colloidal associate solutions on surfaces in the form of flat structures of various kinds. You usually get completely homogeneous, shiny, in particular Cases also micro-heterogeneous, matt coatings. With very hard products powder can also be obtained by drying or spraying the latex.

For the preparation of the used as starting material for the dispersion Ionic polyurethane compositions present in organic or organic-aqueous solution have essentially been taken in two ways: A. The production of the containing high molecular weight, nonionic, for example basic nitrogen atoms Polyurethane mass takes place in a known manner without solvents. The received, im general more or less rubbery product will subsequently dissolved in a suitable solvent and then treated with alkylating agents or Acids, optionally in the presence of water, converted into salt form.

B. The structure of the high molecular weight nonionic polyurethane composition from the components takes place in an organic solvent, which optionally can also contain water. Preferably find polar hydrophilic solvents Use in portions with continued. progressive reaction of the polyurethane mass e can be added. After the polyaddition has ended or is at least largely completed is alkylated or converted into salt form with acids.

It has been shown that route A is not feasible in many cases and also route B, especially with large batches of over 20 kg, considerable difficulties prepares so that the desired ionic polyurethane solutions according to the prior Technology could not be produced on a large scale.

The difficulties arise particularly in the manufacture of hard Polyurethane compositions with a high content of urethane groups, but also z. 3. when using linear polythioethers free of methyl groups and lack solubility the like polyurethanes and in particular their salt-like reaction products in the preferred organic solvents used.

When producing an adduct, for example from 25% of a polyester diol (OH number 65), 18% of a mixture of linear low molecular weight glycols, 7 ovo Methyl diethanolamine and 50% toluene diisocyanate are the first that arise relatively low molecular weight reaction products are clearly soluble in acetone. With advancing Reaction, recognizable by the increase in viscosity, the solution becomes more and more cloudy; at the same time the ability to absorb more acetone decreases. A 45% Polyurethane solution in acetone with a viscosity of 200 stokes shows when stirred silvery streaks, tends to form layers and no longer absorbs acetone. One such inhomogeneous solution can no longer be uniform and reproducible with alkylating agents quaternized, as an acetone solution of the ouaternier (rrrgimtttel a second Phase forms and the solubility of the polyurethane mass due to the quaternization the interface drops abruptly. The addition of, for example, dimethyl sulfate without Solvent is not possible, however, as this would result in homogeneous mixing already locally limited reaction sets in as a result of the formation of reaction products reduced solubility with de-swelling makes homogeneous incorporation impossible.

The difficulties can be solved by using solvents deal with better dissolving power, e.g. tetrahydrofuran or dimethylformamide, or through the use of intensive stirrers for heterogeneous reaction mixtures. deal with. However, these means are uneconomical and technically inexpedient. Because the solvents used up easy way in the following Reaction step of dispersion must be replaced by water, they should can be regenerated easily and without water in a simple manner. These Conditions are poorly met by tetrahydrofuran and not met by dimethylformamide. Finally, intensive stirrers for the highly viscous masts at hand are technical complex and require expensive special equipment.

It has now been found that the difficulties described in a simple and economical manner even when using low-boiling solvents Avoid using the alkylating agent during the reaction between the polyhydroryl compounds, polyisocyanates and chain extenders, and although immediately after the addition of the chain extenders, as long as the viscosity of a 60-point solution is still below 7,000 cP / 250, adds.

The invention accordingly relates to a method of production of polyurethane plastics, including fabrics or adhesion promoters according to the diisocyanate polyaddition process with a content of 0.22-2% quaternary ammonium groups based on compounds with reactive Hydrogen atoms with a molecular weight of 300-20,000, polyisocyanates and Chain extenders with at least two reactive hydrogen atoms, wherein at least one chain extender is at least a) a tertiary basic Nitrogen atom or b) at least one reactive halogen atom or one -SO2-O-R group contains, as well as in case a) alkylating agents and / or acids or in case b) tertiary Amines, and solvents, which is characterized in that you have so much of / the Alkylating agents and / or acids or the tertiary amine during the between the polyhydroxyl compounds, polyisocyanates and chain extenders taking place Reaction immediately after combining at least 80% of the remaining reactants added as long as the viscosity of a 60% own solution is still below 7,000 cP / 250, that the content of quaternary ammonium groups is at least 0.21 M0 and optionally after further addition of acid and, if necessary, transfer of the dissolved polyurethane mass in a manner known per se into a latex or an aqueous colloidal solution any point in time the organic or aqueous solution or

Dispersant removed.

Such a mode of operation offers compared to the method according to prior art technology has a number of advantages. At the time all reactants are added there is now a completely homogeneous reaction medium which is thoroughly mixed guaranteed even with simple anchor stirrers at low speed. The one with increasing Molecular weight decreasing solubility is now completely continuous, whereby the inhomogeneity of the mixture that occurs in the later reaction section to the outside is far less apparent, d. H. there is no stratification and no uneven stirring.

Surprisingly, even now pronounced bad solvers can be found z. B. chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane, dichloropropane, use as reaction medium, being more or less cloudy to completely opaque weirje "solutions" arise, which undoubtedly are not real solutions in the narrower sense, but represent more or less dispersions, colloid solutions or plastisols. The possibility of using such solvents is due to their incombustibility, their low boiling point and the low heat of evaporation are technically advantageous. Despite their insolubility in water, these solutions can be used just as well Prepare aqueous dispersions such. B. from acetone solution. Your anhydrous recovery however, it is much easier.

Another advantage over the prior art methods is the shortening of the overall reaction time achieved. This is not just the case so far The time required for the quaternization process is saved, but it is done additionally a catalytic acceleration of the isocyanate polyaddition. For very long Alkylations with less reactive alkylating agents such as benzyl chloride conditional the early addition of the alkylating agent at the time of a higher polyurethane concentration also an acceleration of the alkylation process.

Another advantage is one in the method according to the invention flawlessly possible viscosity control during the reaction leading to reproducible Manufacture of type-compliant products is necessary. Such a viscosity control is only possible in a largely homogeneous reaction medium.

Finally, latices that are produced from according to the invention stand out Solutions were obtained by special fine division from what z. B. for high-gloss coatings is desirable.

DAS 1 168 070 describes a process for the production of hydrophilic Using polyurethane foams made from polyesters, polyisocyanates and water of polyesters containing tertiary nitrogen atoms, the reaction in the presence a quaternizing agent optionally used together with a polyisocyanate for tertiary nitrogen atoms. This causes the reaction with the quaternizing agent an increase in the hydrophilicity of the end product, resulting in increased water absorption expresses.

However, the procedure according to the invention can be derived from this teaching cannot be derived, as the content and purpose of the two procedures are completely different are. The production of foams is described in the cited patent application. So it is a reaction that takes fractions of a minute A cross-linked, porous polyurethane plastic is created directly from the components. In this case, all reaction components must necessarily be combined at the beginning, so in the present Case also the alkylating agent. This means but not that the alkylation is simultaneous with the diisocyanate polyaddition he follows. This is the case with the examples cited in the cited publication not the case, as benzyl chloride and allyl chloride compared to basic polyesters are relatively inert alkylating agents, which even at elevated temperature only in the Respond over the course of several hours. The received Foams are reheated. Any influencing of the Isocyanate reaction due to the alkylation, for example with regard to the degree of crosslinking would not appear at all.

This is in contrast to the method according to the invention around - the structure of very high molecular weight, predominantly linear, non-crosslinked polyurethanes in organic solution, with the early addition of the alkylating agent mainly serves to avoid a heterogeneous reaction and thus technical advantages in the production of the ionic polyurethane solution and, if appropriate, produced therefrom aqueous dispersions brings with it. As is well known, the production is of high molecular weight linear polyurethanes a very sensitive reaction to additives, which is why It was not a matter of course that one would without danger those under construction Polyurethane chains can also quaternize, especially since the catalytic effectiveness of the quaternary ammonium group on the isocyanate polyaddition is known.

The Belgian patent 653 223 describes the production of polyurethane compounds known with a maximum of 0.2% quaternary nitrogen, either for their production a salt-forming component (e.g. a tertiary amino diol) or a salt-like one Component (e.g. a quaternary ammonium diol) can also be used. These components can be added at any time during the reaction. It is also possible to generate the salt-like component in situ by using together with the salt-forming component has a salt-forming counter component (e.g. a quaternizing agent such as dimethyl sulfate) is added. The time at which the quaternizing agent is added is irrelevant here, since on the one hand it is only a relatively small amount of quaternizing agents (the content of quaternary ammonium groups should not be 0.2% exceed) acts, on the other hand, the molecular weight of the polyurethane mass the dispersion need not be high and also the presence of solvents is not required. The NCO / OH ratio can vary between 0.4 and 1.5.

In contrast, it is within the scope of the present invention in order to avoid larger amounts of alkylating agents in connection with solvents, especially also relatively poor solvents are used. Of the Quaternary ammonium nitrogen content of the polyurethane mass (calculated without solvent) before dispersing should be over 0.22%. Continue to be preferably made of high molecular weight polyurethane compositions, which as 45 OJoige solution have viscosities between 2,000 and 80,000 cP / 250, indicating molecular weights of over 20,000. This is where the tendency towards the formation of Two-phase systems play a role during quaternization.

Furthermore, it is within the scope of the present invention and in contrast Regarding the teaching of Belgian patent 653 223, it is by no means indifferent to which one Time the addition of the quaternizing agent takes place. So is the encore together unfavorable with the basic chain extender or after pre-reaction with this, because in the case of sufficiently reactive components such as N-methyldiethanolamine and dimethyl sulfate instantly high-melting and poorly soluble in organic solvents Form quaternary ammonium salts, which under certain circumstances precipitate in crystalline form and become withdraw from further reaction. When using bifunctional alkylating agents Tetrafunctional chain extenders can easily be formed, the swelling of the reaction mixture can result. On the other hand, the quaternization reaction should also do not use too late, otherwise solubility and stirring problems will occur again.

It has been found that the addition of the quaternizing agents works best immediately follows the addition of the chain extenders, as long as the viscosity of a 60% own solution is still below 7,000 cm / 25, on the other hand the basic chain extender already in the Polyaddition reaction has been included. In addition to or in place of the quaternizing agents Salt-forming acids can also be used.

The compounds suitable for the process according to the invention with several reactive hydrogen atoms are essentially linear and have a molecular weight of 300-20,000, preferably 500-6,000.

These known compounds have terminal hydroxyl, Carboxyl, amino or mercapto groups; polyhydroxyl compounds are preferred such as polyesters, polyacetals, polyethers, polythioethers, polyamides and polyester amides.

As polyethers are z. B. the polymerization products of ethylene oxide, Propylene oxide, tetrahydrofuran, butylene oxide and their mixed or graft polymerization oducts as well as those resulting from the condensation of polyhydric alcohols or mixtures the same and those by alkoxylation of polyhydric alcohols, amines, polyamines and amino alcohols called polyethers. Also isotactic polypropylene glycol can be used.

As polyacetals, for. B. those made from glycols such as diethylene glycol, Triethylene glycol, 4, -Dioxäthoxy -diphenyl- di methylm ethane, hexanediol and formaldehyde possible connections in question. Also by polymerizing cyclic acetals suitable polyacetals can be produced.

Among the polythioethers are in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, Formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components the products are polythioethers, polythio mixed ethers, polythioether esters, Polythioether ester amides. Such polyhydroxyl compounds can also be alkylated Form or in a mixture with alkylating agents are used.

The polyesters, polyester amides and polyamides include those made of polyvalent ones saturated and unsaturated carboxylic acids or their anhydrides and polyvalent ones saturated and unsaturated alcohols amino alcohols, diamines, polyamines and Mainly linear condensates obtained from their mixtures, as well as polyterephthalates, for example or polycarbonates.

Also polyesters made from lactones, e.g. B. £ -caprolactone, or from hydroxycarboxylic acids are usable. The polyesters can have hydroxyl or carboxyl end groups. For their structure, higher molecular weight polymers or can be used as alcohol component Condensates such as B. polyethers, polyacetals, polyoxymethylene (with) can be used.

Also polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols such as castor oil, carbohydrates are usable. In principle, there are also polyhydroxyl compounds, which are basic Have nitrogen atoms, in question »z. B. polyalkoxylated primary amines or polyesters or polythioether, which contain condensed alkyl diethanolamine. Compounds with reactive halogen atoms can also be condensed in, e.g. B.

Glycerin - # - chlorohydron. Such compounds can also be used in alkylated, d. H. Onium form if present in the preparation of the reaction products other components are also used, the quaternizable groups for the invention Procedure included.

To vary the lyophilicity or the hydrophobicity and the mechanical Properties of the process products can be mixtures of different polyhydroxyl compounds can be used. Suitable higher molecular weight compounds with amino end groups are z. B. in French patents 1 361 810, 1 300 981, DAS 1 122 254 and U.S. Patent 2,888,439.

All aromatic and aliphatic diisocyanates are suitable as polyisocyanates suitable, such as B. 1, 5-naphthylene diisocyanate, 4, -diphenylmethane diisocyanate, 4, 4 '-Diphenyldimethylmethane diisocyanate »Di- and tetraalkyldiphenylmethane diisocyanate, 4, 4'-dibenzyl diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, the Isomers of toluene diisocyanate, optionally in a mixture, l-methyl-2,4-diisocyanato-cyclohexane, 1, 6 diisocyanato-2, 2, 4-trimethyl-hexane, 1, 6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1, 5, 5-trimethyl-cyclohexane, chlorinated and brominated Diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, Tetramethoxy-butane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane 1, 6-diisocyanate, dicyclohexyl methane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene dii socyanate, phthalic acid bis-isocyanatoethyl ester, and also polyisocyanates with reactive 1-halogen atoms, such as 1-chloromethylphenyl1-2, 4-diisocyanate, 1-bromomethylphenyl- 2,6-diisocyanate, 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate. Sulphurous Polyisocyanates are obtained, for example, by reacting 2 moles of hexamethylene diisocyanate with 1 mole of thiodiglycol or dihydroxyl sulfide.

Partially disguised polyisocyanates deserve particular interest, which allow the formation of self-crosslinking polyurethanes, e.g. B. dimeric toluene diis ocyanate, or with slightly white phenol, tertiary butanol, phthalimide, caprolactam partially converted polyisocyanates.

To the chain extenders with reactive hydrogen atoms include: 1. the usual saturated and unsaturated glycols, such as ethylene glycol or condensates of ethylene glycol, 1,3-butanediol, 1,4-butanediol, butenediol, propanediol-1, 2, propanediol-1, 3, neopentyl glycol, ilexanediol, bis-hydroxymethyl-cyclohexane, Dioxäthoxyhydroquinon, Dioxäthyldiane, Terephthalic acid-bis-glycol ester, Succinic acid-di-ß-hydroxyethyl-amide, Succinic acid di [N-methyl- (ß-hydroxy-ethyl)] amide, 1,4-di (ß-hydroxy-methyl-mercapto) -2,3,5,6-tetrachlorenzene, 2-methylenepanediol- (1,3), 2-methyl-propanediol- (1, 3) 2. aliphatic, cycloaliphatic and aromatic diamines such as ethylenediamine, hexamethylenediamine, 1, 4-cyclohexylenediamine, benzidine, diamino-diphenylmethane, dichloro-diamino-diphenylmethane, the isomers of phenylenediamine, hydrazine, ammonia, carbohydrazide, adipic acid dihydrazide, Sebacic acid dihydrazide, piperazine, N - methyl - propylenediamine, diaminodiphenyl sulfone, Diaminodiphenyl ether, diaminodiphenyldimethyl methane, 2,4-diamino-6-phenyltriazine; 3. Amino alcohols such as ethanolamine, propanolamine, butanolamine, N-methylethanolamine, N-methyl-isopropanolamine; 4. aliphatic, cycloaliphatic, aromatic and heterocyclic mono- and diaminocarboxylic acids such as glycine, # - and ß-alanine, 6-aminocaproic acid, 4-aminobutyric acid, the isomeric mono- and diaminobenzoic acids, the isomeric mono- and diaminonaphthoic acids; 5. water.

There are also less common, such. B. high-melting chain extenders with reactive hydrogen atoms in the context of the present process, such. B. 4, 8 -Di- (N-methyl-ß-hydroxyäthylamino) -diphenylmethane, ethyl-bis-3-hydroxy-cyclohexyl-phosphine oxide, N, NO -dimethyl-ethylene-diamine, oxalamidrazone, oxalic acid-bis-ethanolamide, 2,6-di- (hydroxymethyl) -tetrahydropyran, di- (hydroxy-neopentylidene) -pentaerythritol, dimethylol-tetrahydro-pyrimidine-thione, N, N, -bis - (2 - aminoethyl) oxalic acid amide, N, NO - Bis (2 -amino-propyl) oxalic acid amide, dioxydiethyl sulfone, 4-methylamino-butanol- (2), N, - -carboxybutylurea, methylenebisbenzoic acid, methylenebisbenzyl alcohol, hexane bis-semicarbazide '# - Hydroxybutyric acid hydrazide, 6-aminocaproic acid hydrazide, phenylglycol, dim ethyloldihydropyran, dimethylol tetrahydrofuran, tetrachlorobutanediol, dithiooxamide, pentaearythritol mono-acetone ketal, pentachlorophenylglycerol, di- hydroxymethyl) - # 3-cyclohexene, lauric acid di (hydroxyethyl) amide, isobutylidene diureide, also the compounds: HO (CH2) 2-NH-CO-CO-NH- (CH2) 6-NH-CO-CO-NH (CH2) 2-OH CH3 CH3 CH3 CH3 HO-CH2-C-CO-O-CH2-C-CH2-OH HO-CH2-C-CO-NH-CH2-C-CH2-OH CH3 CH3 CH3 CH3 HO- (CH2) 2-CO-NH- (CH2) 6-NH-CO- (CH2) 2-OH. I3. The formation of salts in basic chain extenders results in particularly high strength and water resistance, even when exposed to moisture and solvents.

It should be emphasized that this is not strictly within the scope of the present invention between the compounds having reactive hydrogen atoms with a molecular weight from 300 to 20,000 and the so-called "chain extenders" ' since the transitions between the two connection classes are fluid. Compounds that are not built up from several monomer units, but one Have molecular weight over 300, such as. B. 3, 3'-dibromo-4, 4'-diaminodiphenylmethane, are counted among the chain extenders, but also pentaethylene glycol, although the composition of the latter is actually a polyether diol.

Special chain lengthening agent with at least one basic one Nitrogen atom are e.g. B. mono-, bis- or polyoxalkylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, such as N-methyldiethanolamine, N-ethyl-diethanolamine, N-propyl-diethanolamine, N-isopropyl-diethanolamine, N-butyl-diethanolamine, N-I sobutyl-diethanolamine, N-oleyl-diethanolamine, N-stearyl-diethanolamine, oxethylated coconut fatty amine, N-allyl-diethanolamine, N-methyl-diisopropanolamine, N-ethyl -diisopropanolamine, N-propyl-diisopropanolamine, N-butyl-diisopropanolamine, N-cyclohexyl-diisopropanolamine, N, N-dioxäthylaniline, N, N-Dioxäthyltoluidin, N, N Dioxäthyl - # - aminopyridin, N, N'-Dioxäthyl-piperazin, Dimethyl-bis-oxäthylhydrazine, N, N'-bis- (ß-hydroxy-ethyl) -N, N'-diethyl-hexahydro-p-phenylenediamine, N-ß-hydroxyethyl piperazine, polyalkoxylated amines such as oxpropylated Methyl diethanolamine, also compounds such as N-methyl-N, N-bis- # -aminopropylamine, N - (# - aminopropyl) -N, N'-dimethylethylenediamine, N - (# - aminopropyl) -N-methyl-ethanolamine, N, N'-Bis - (# - aminopropyl) -N, N'-dimethylethylenediamine, N, N'-bis - (# - aminopropyl) -piperazine, N- (ß-aminoethyl) -piperazine, N, N'-bisoxäthyl-propylenediamine, 2,6-diaminopyridine, diethanolamino-acetamide, diethanolamidopropionamide, N, N-bis-oxäthylphenyl -thiosemicarbazid, N, N -Bis -oxäthyl -methyl- semicarbazid, p, p '-Bis-aminomethyl-dibenzylmethylamine, 2,6-diaminopyridine, 2-dimethylaminomethyl-2-methyl-propanediol-1,3.

Chain extender with halogen atoms capable of quaternizing or R-S020 groups are, for example, glycerine - # - chlorohydrin, glycerine monotosylate, pentaerythritol bis-benzenesulfonate, glycerol monomethanesulfonate, adducts of diethanolamine and chloromethylated aromatic isocyanates or aliphatic halogen isocyanates such as N, N-bis-hydroxyethyl-N'-chloromethylphenylurea, N-hydroxyethyl-N'-chlorhexylurea, Glycerin mono- chloroethyl urethane, bromoacetyl dipropylenetriamine, chloroacetic acid -diäthanolamidj It is possible, in addition to the mentioned predominantly bifunctional Reaction components in amounts of up to 10% for components with a molecular weight over 1000 up to 30%, tri- or higher functional components to be used, e.g. B. branched polyester or polyether, occurs and higher functional Isocyanates such as Tris-isocyanatohevl-biuret or cyclic isocyanurate pligomers from Diisocyanates. More highly functional chain extenders can be used just as well like glycerine, trimethylolpropane, pentaerythritol, dipropylenetriamine, hexanetriol, Triethanolamine.

The following are examples of monofunctional alkylating agents: Methyl chloride, methyl bromide, methyl iodide, ethyl bromide, propyl bromide, butyl bromide, Dimethyl sulfate, diethyl sulfate, methyl chloromethyl ether, methyl 1,2-dichloroethyl ether, Ethyl chloromethyl ether, benzyl chloride, benzyl bromide, p-chlorobenzyl chloride, trichlorobenzyl chloride, p-nitrobenzyl chloride, ethylene chlorohydrin, ethylene bromohydrin, EpicKorhydrin, ethylene oxide, Propylene oxide, styrene oxide, benzene, toluene, naphthalenesulfonic acid esters' # -Bromoacetophenone, Dinitrochlorobenzene, # -chloropentenamide, chloroacetic acid and their esters and amides, Chlormethyldlmethyl- ethoxysilane, pentamethylchloromethyldisiloxane, pentamethylbromomethyl-disiloxane, Glycol monobromoacetic acid ester, glycerine monochloroacetic acid ester, bromine ethyl isocyanate, Chloromthyl naphthalene, 3-methyl-3-hydroxymthyl oxetane methanesulfonate, phenylethyl bromide, p-2-bromoethylbenzoic acid, 5-chloromethyl-furan-2-carboxylic acid, ethylphosphonous acid dichloroisopropyl ester, Bromoethyl acetoacetate. Further examples can be found in DAS 1 205 087.

Quaternization can also be carried out with cyanogen chloride or cyanogen bromide will. Epoxides are used in combination with water and / or an acid as a quaternizing agent used.

Tertiary amines suitable for quaternization include trimethylamine, Triethylamine, triethanolamine, dimethylaminoethanol, N-methyl-diethanolamine, pyridine, Quinoline, N-dimethylaminopropyl diethanola min mentioned by way of example.

Even acids can form salts at this stage of the reaction are used, preferably those that also have a chain-building end Exercise function, such as B. sulphurous acid, sulfuric acid, hypophosphorous acid, phosphorous acid, phosphoric acid and their mono- and diesters, phosphinic acids, phosphonous acids and phosphonic acids, glycolic acid, lactic acid, succinic acid, tartaric acid, oxalic acid, Phthalic acid, trimellitic acid.

The abovementioned compounds are reacted in accordance with known methods Procedure. The order in which the components are put together is irrelevant. The amount of polyisocyanate can be in excess or deficiency or in equivalence to the reactive hydrogen atoms of the polyhydroxyl compound used and optionally the chain extender. Preferably is the NCO-OH ratio 0.8 1 to 1.4: 1. The chain extenders are preferred or at least part of it admitted last. The alkylation or salt formation takes place immediately after combining at least 80% of the remaining reaction participants, as long as the viscosity of a 60-point solution is still below 7,000 cP / 250, on the other hand the chain extender capable of the alkylation reaction in the polyaddition reaction is included. The solution is at the time of addition of the alkylating agent (s) or of the amine or amines, preferably 60-85% of the remaining reactants or their conversion products. For example, one is suitable for the alkylation 70% solution with a viscosity of 100,000 cm / 25, as this, diluted to 60%, has a viscosity of less than 7,000 cP / 250. The alkylation can also be more dilute Solutions are carried out when their viscosity is correspondingly low.

The following table shows the relationship between concentration and Viscosity at reaction temperature or at room temperature. (The addition of polyurethane corresponds to example 1 - 4.) Concentration viscosity at viscosity at reaction temperature Room temperature (400) (250) 70% 120,000 cP 400,000 cP 60% 4,000 - 5,000 cP 18,000 cP 50% 600 - 800 cP 1 900 cP 45% 300 - 400 cP 980 cP 40% 150 - 180 cP 400 cP the Viscosities were measured with the rotary viscometer. It is about the after about two minutes the viscosity sets in, which, depending on the speed, is somewhat fluctuates.

Between the union of at least 80% of the remaining reactants and the alkylation will generally last from 2 to 70 minutes, depending on Reactivity of reactants and content of solvent. Slow responsive Alkylating agents, such as. B.

Butyl bromide, benzyl chloride, can be used immediately after the remaining reactants are added, while strong alkylating agents such as dimethyl sulfate, methyl bromide, methyl - chloromethyl ether only expediently be added to the reaction mixture after some time. Are more weakly basic or sterically unfavorable tertiary amino groups in the reaction mixture, for. B. if butyldiethanolamine or dioxäthylaniline are incorporated, strong alkylating agents can also be used can be added immediately to the reaction mixture without further ado. With strong bifunctional or polyfunctional alkylating agents, such as. 3. p-xylylene dichloride, depends the time of addition also from the time of transferring the reaction solution into the aqueous phase. It should have a crosslinking effect of the polyfunctional Alkylating agent largely before and during the transfer into the aqueous phase be avoided.

According to a preferred mode of operation, the connections are first with reactive hydrogen atoms and a molecular weight of 300 to 20 000 with the total amount or a predominant proportion of the diisocyanates solvent-free reacted and then successively the chain extenders and alkylating agents added together with part of the solvent used. With advancing Reaction is further solvent and optionally also diisocyanate or Kettenv extension means added.

Polar low-boiling solvents are primarily used as solvents in question, such as acetone, methyl ethyl ketone, diisopropyl ketone, dioxane, tetrahydrofuran, Acetonitrile, ethyl acetate, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, 1, l-dichloroethane, 1, 2-dichloropropane, if given in a mixture with non-polar solvents such as benzene, toluene, carbon tetrachloride. Of course are also high-boiling solvents such as dimethylformamide, di methylacetamide, dimethyl sulfoxide, Tetramethylene sulfone, optionally mixed with non-polar solvents, suitable, but the use of such solvents only makes sense if the polyurethane mass not subsequently converted into an aqueous dispersion or colloidal solution or the presence of such solvents in the aqueous dispersion is desirable is z. 3. to favor film education.

In this sense, solvents can also be used at 400 liquid Soft macilwr can be understood as e.g. B. phosphoric acid triester, phthalic acid ester, Oil alkyds, higher molecular weight polyesters and polyafers, fatty oils or (chlorinated ' higher carbons.

On the other hand, polyurethane compositions with a lower content of ammonium groups can be used (e.g. Ob 22 - 0> 4%). and low content of urethane groups also in less polar ones Solvents are produced e.g. B. in ether, benzene, toluene, xylene, also in Mixtures containing large amounts of aliphatic hydrocarbons.

The solvents used only need those for the implementation to solve brought reaction participants and / or the initially formed still relatively low molecular weight polyurethane pre-adduct, but not the high molecular weight salt-like one Polyurethane compound that is formed in the course of the reaction. The here as "solutions" designated distributions of the polyurethane composition in solvents can accordingly have very different characters. It can be real molecular solutions, colloidal solutions of associates, plastisols or stable dispersions of polyurethane act in the solvent.

Also swollen, gelatinized or softened with the solvent Polyurethane compounds made flowing or at least plastic in this way can be understood under these "solutions".

This latter case is often realized in practice, since e.g. 3. Ionic polyurethane compositions with a high content of urethane groups very often from z. 3. Acetone, dioxane, ethyl acetate, halogenated hydrocarbons are not dissolved, however, for their part, up to 100% of these solvents are able to be absorbed and thus can be processed like solutions.

The amount of the total solvent used is generally between 10 and 600% of the weight of the polyurethane mass.

Surprisingly, bifunctional or polyfunctional ones can also be used Quaternizing agents in addition to the monofunctional quaternizing agents mentioned or use in their place if the solutions are subsequently converted into aqueous dispersions or colloidal solutions are transferred. Such bis or polyfunctional quaternizing agents initially react monofunctionally and can be incorporated into polyurethane compounds, which become self-networking in this way.

The polyfunctional alkylating agents used contain at least two reactive halogen atoms or R-SO2O groups, in which R is an alkyl or Means aryl radical. Examples are: 1,3-dibromobutane, 1,4-dibromobutane, 3-trichloroisobutane (only two chlorine atoms are reactive), 1,6-dibromohexane, 1,3-dibromoneopentane, methylhexanediol ditosylate, 1,3-bis-chloromethyl-4, 6-dimethyl-benzene, o-, m-, p-xylylene dichloride, bischloromethyl -naphthalene, bis-chloromethyl-diphenyl ether, bis-chloromethyldurol, bis-chloromethyl-tetrachlorobenzene, 1, 3, 5-tris-chloromethyl-2, 4, 6-trimethylbenzene, 3, 4-bis-chloromethyl-toluene, 2, 4-bis-chloromethyl-toluene, 1, 4-dibromo-2, 3-dihydroxy-butane, 4, 41-bis-chloromethyl-diphenyl, 9, 10-bis-chloromethyl-anthracene, 1,3-bis-bromomethyl-benzene, 3, 3-bis-bromomethyloxa-cyclobutane, 2, 2, -p-phenylenedioxy diethyl bromide, 4, 41-bis-chloromethyl-diphenylmethane, 1, 4-dibromobutene- (2), 1, 2, 3, 5-tetrakis-chloromethylbenzene, tetrachloro-p-xylylene dichloride, 1,2,3,4-tetrakis-chloromethylbenzene, 2, 6, 2's 6'-tetrakis-bromomethyl-diphenyl, 1, 5-dibromo-3, 3-dicyanopentane, 2,4,6-tris-chloromethyltoluene, 3,4,5-tris-chloromethyltoluene, 2,3,4,5-tetrakis-chloromethyltoluene, 2, 3, 4, 5, 6-pentakis-chloromethyl-toluene, Di- [p- (chloroacetyl) phenyl] ether, 1,4-bis-bromomethyldiphenyl ether, 1,4-dichlorobutene, 1,4-dichlorobutine, dichloromethyl ether, dichloroethyl ether, dibromobutyl ether, dichlorodiethyl sulfide, Dibromodithylsulfid, Tris-chloräthylsulfonium chloride, Dichlordiäthylsulfon, 9, 10 - dichloranthracene, cyanuric chloride, tris-chlorhexyl isocyanurate, adipic acid bis-ß-bromoethyl ester, Succinic acid bis-ß-chloroethyl ester; haloacylated polyamines such as bischloroacetylhydrazine, Bis-chloroacetyl-N, N'-dimethylhydrazine, methylene-bischloroacetamide, methylene-bis -bromoacetamide, bis-cbloracetyl-ethylenediamine, 1,2-bis- (monobromoacetoxy) -ethane, Bis-chloroacetyl-N, N'-dimethylethylenediamine, bis-chlorcety1piperazine, bis-bromoacetyltetramethylenediamine> Bischloroacetylhexamethylenediamine, bis-bromoacetyl hexamethylenediamine, bischloropropionylpiperazine; Bis-urethanes from difisocyanates and bromoethanol, such as 4,4'-methylene-bis-carbanilic acid-bis-bromoethyl ester, hexamethylene bis -bromoethyl urethane, toluylene - 2, 4 - bis -bromo ethyl urethane, T. oluylene-2,6-bis -bromo ethyl urethane, hexamethylene-bis-chloromethyl-phenylcarbamic acid ester, Tetramethylene-bis-chloromethylphenylurea, #, # '- dichloroacetone, 3, 3-bis - (brom m ethyl) - oxacyclobutane, 1, 3-dichloro - 2, 2-bis - (p - hydroxyphenyl) -propane, 2,2 '- (p-phenylene-dioxy) -diethyl bromide, N, N-bis-bromoethyl-aniline, 1,3-dibromobutyric acid amide, 2-chlorobenzylidine-bis-chloroacetamide, 3, 8-bischloromethyl -5-hydroxy-4-methylcoumarin-6-carboxylic acid methyl ester, 2,2-bis-chloromethylpropanediol, tri-bromo-neopentane, glycerine bis-tosylate, glycerine tris-tosylate, Trimthylolpropane-tris-ethanesulfonate, Diphenylätherp, p'-dibenzenesulfonat, Athy.en-di-p-toluylensuStonat, chloromethylated polystyrene, chloromethylated polycarbonates, poly- [bis- (3,3-chloromethyl) oxetane7, Polyvinyl chloroacetate; Polymers that contain as co-monomer: chloroacetyl methacrylamide, N, N-bis-ß-chloroethyl-acrylamide, 3-chloropropene- (1) -yl-acrylamide, acrylic acid-ß-bromoethyl ester, Vinyl 2-chloroethyl ether, 1,3-bis-chloromethyl-1,1,3,3-tetramethyldisiloxane, 1,3-bis-bromomethyl-1,1,3,3-tetramethyldisiloxane, Bis-bromomethyl-polysiloxane, glycol-bis-chloroacetic ester, glycerol-bis-chloroacetic ester, Bis-bromomethyl-diphenyl ether, di-chloroethyl-formal, 3, 7-dichloromethyl-6-metoxy-4-methylcoumarin, Benzylidene-bis-chloroacetamide, ethylidene-bis-chloroacetamide, bis-bromoethyl disulfide, Di- [p- (chloroacetyl) phenyl] ether, 2-bromopropylbenzyl bromide, glycol bis-chloromethyl ether, 1> 6 -hexanediol bis-chloromethyl ether, 1,4-butanediol bis-chloromethyl ether, hydroquinone bis-chloromethyl ether.

The amount of mono and! or polyfunctional alkylating agent depends on the number of basic tertiary nitrogen atoms available, However, it should be noted that in the finished solvent-free polyurethane plastic the quaternary ammonium nitrogen content is between 0.22 and 2%. It is also the Including the proportion of ammonium nitrogen caused by the reaction with an acid whose pK value is less than 4 was generated.

Generally only a fraction, e.g. B. 5 - 80% of the existing tertiary nitrogen atoms are alkylated by quaternizing agents, the remainder remains for the later self-crosslinking or the formation of salts by acids.

Analog can be used for the immediate or later molecular enlargement of Polyurethanes, for the structure of which compounds with reactive chlorine, bromine or Sulphonic acids were used, in addition to quaternizable tertiary monoamines di- or polyamines are also used, such as. B. 1, 4-Diaza-bicyclo-82, 2, 2] -octane, Tetramethylethylenediamine, tetramethyl-propylenediamine, tetramethyl-hexamethylenediamine, Pentamethyldipropylenetriamine, hexamethyl-triethylenetetramine, 1,4-bis-dimethylaminomethyl-benzene, Hexamithylene-bis-carbamic acid-bis-dimethylamino-ethyl ester, #, # '- dipyridyl, #, #' - dipyridyl, Dihydroxy-1,4-dipyridyl- (3 ') - butane, adducts of dimethylaminoethanol or N, N-dimethylajylenediamine to polyisocyanates. Other suitable polyamines are, for. B. in the Belgian patent 636 799 included.

After all of the reactants have been added, the solvent-containing substances are left in Polyurethane mass at room temperature or elevated temperature, preferably at 40 - 80 °, react until the desired viscosity is reached. If necessary, still isocyanate groups present can by adding small amounts a chain terminator, e.g. B. an alcohol, primary or secondary amine or a carboxylic acid. be locked.

When using bis or polyfunctional alkylating agents However, this measure alone does not guarantee a constant viscosity. In this case, however, a very slow one takes place over the course of days Molecular weight increase through quaternizing chain extension. This can be for the reproducible setting of very high molecular weights. As is well known is the reproducible setting of very high molecular weights solely through isocyanate polyaddition difficult and often impossible, since such approaches easily become too high molecular jellyfish and are therefore unusable. In such cases it is useful to use the Isocyanate polyaddition only up to a certain easily achievable viscosity to drive and to bring it to the end by means of bifunctional quaternizing agents. the Reaction. can then be reversibly stopped by adding acid.

The described reaction procedure is particularly suitable when used technical water-based solvent and subsequent transfer of the polyurethane mass in aqueous dispersion. To achieve finely divided dispersions with medium particle diameters Below 500 mr to 50, the polyurethane mass at the time of adding water should if possible no contain more free isocyanate groups, but have a high molecular weight be. On the other hand, there are slight fluctuations in the water content of technical solvents unavoidable, which thus affect the diisocyanate polyaddition.

After all, it is desirable to have only a fraction of that in the solvent incorporated water into the polyurethane mass by isocyanate reaction. In fact, a polyaddition proceeding with an enlargement of the molecule can also be carried out perform in the presence of excess water in the solvent, but is the The end point of the reaction is then indefinite and may be considerably below that the desired molecular weight range. By using bifunctional alkylating agents, which are incorporated monofunctionally during the diisocyanate polyaddition and im Subsequent to this, also react in the presence of water with molecular linkage, can be flawless even under the unfavorable conditions described represent reproducible high molecular weight polyurethane compositions free from swelling.

The same applies mutatis mutandis to the alkylation of reactive halogen atoms or polyurethanes containing sulphonic ester groups with di- and polyamines, such as Tetramethylethylenediamine, pentamethyl-diethylenetriamine, pentamethyl-dipropylenetriamine, Hexamethyl-triethylenetetramine, diazabicyclooctane, dimethyl-piperazine.

In a preferred procedure, the high molecular weight quaternized, Solvent-containing polyurethane composition then into an aqueous dispersion or transferred to a colloidal aqueous solution.

For this purpose, it is sufficient to use the solvent-containing polyurethane quantity at room temperature, but preferably at a higher temperature, e.g. B 40 - 1000, water to add. Depending on the chemical composition, the degree of alkylation, the concentration of the starting solution, the amount of water added and the method the conversion into the aqueous phase gives colloidal aqueous solutions, aqueous ones Dispersions or unstable suspensions or pastes.

If the alkylated polyurethane mass still has free basic nitrogen atoms contains, the dispersibility can be mono- or by adding small amounts improve polyfunctional acids. It is also advisable to add acid when present polyfunctional alkylating agents in order to take part in a further reaction during the To prevent the dispersing process.

Finally, the properties of the solutions or Polyurethane plastics obtained from dispersions by the type and amount of added Affect acid.

Preferred acids used are e.g. B. hydrochloric acid, hydrofluoric acid, nitric acid, sulphurous acid, sulfuric acid, hypophosphorous acid, phosphorous acid, phosphoric acid, Polyphosphoric acid, sulfamic acid, hydroxylamine sulfones §Ra, formic acid, Acetic acid, glycolic acid, lactic acid, chloroacetic acid, acrylic acid, benzoic acid, salicylic acid. Further suitable acids are, for example, in DAS k 178 586 and 1 179 363 and listed under the monofunctional alkylating agents mentioned above.

The use of acids with a pK value below 4 generally has an increase in hardness, adhesive strength, toughness, tensile strength, elasticity and The consequence of solvent resistance, often also an increase in hydrophilicity. Polyfunctional Acids act as crosslinking agents, but under certain circumstances this only occurs when the Water becomes effective. Acetic acid affects the properties of the end products least, because they during the drying process as a result of hydrolytic cleavage with the Water escapes. The acids can be dissolved or in an organic solvent can also be added solvent-free to the polyurethane mass. The timing of the Addition is optional, but the reactivity must be more inorganic than organic acids with isocyanate groups can also be taken into account. Slow encore, which leads to a homogeneous distribution is advantageous. In most cases acids are added when the conversion of the polyurethane mass into a Dispersion or colloidal solution is intended. In general then the acids added to the aqueous phase. The acids can be added to the entire amount of water or just a part. Depending on whether the aqueous or the polyurethane phase is initially taken, polyurethane dispersions are obtained with different properties.

According to a preferred procedure, the production becomes more homogeneous Film-forming agents added the acids with a first portion of water, e.g. B. with about 10 - 20% of the total amount of water: For the transfer of the solvents Polyurethane mass in the aqueous phase can be used different methods: So you can simply add water and, if necessary, acids to the polyurethane mass and then or at the same time all or part of the organic solvent remove by distillation. The main advantage of this method lies in its easy implementation. It can be put in and with every vessel in the simplest possible way simplest mixing devices, e.g. B. an anchor stirrer of 30 rpm. accomplish. The dispersion takes place spontaneously in the course of the addition of water or only during the addition the removal of the organic solvent by distillation. The resulting dispersed or colloidly dissolved particles are extremely small, e.g. B. they have a diameter from 20 - 200 m. However, larger particles can also be easily produced.

The resulting particles are uncrosslinked when the polyurethane mass before the addition of water, essentially of NCO groups or compounds with a crosslinking action was free.

By setting a corresponding NCO / OH ratio in the Production of the polyurethane mass or through incomplete reaction can you can easily achieve that at the time of the addition of water the polyurethane mass has a certain content of NCO groups. In this case occurs during the Dispersion process a further molecular enlargement leading to crosslinking. The properties of the end products therefore depend to a large extent on the dispersion process away. Usually agglomerates of cross-linked latex particles are formed. The size of the agglomerates is determined by the rate at which water is added. With increasing rate of addition the dispersion is favored over the crosslinking, so that smaller agglomerates and finally, crosslinked single latex particles are obtained.

In the presence of other, non-water reactive crosslinkable Groups, e.g. B reactive chloromethyl groups formed by the reaction of basic polyurethane compounds has been introduced with a deficit of bifunctional quaternizing agents crosslinked latex particles can also be obtained. Sufficiently hydrophilic However, particles with crosslinking groups remain in the state of the latex for a long time Stably non-networked periods. The self-crosslinking character of the particles comes only take effect during coagulation or when the latex dries up. Self By drying at room temperature, highly crosslinked coatings and fabrics can be produced can be obtained. When transferring free NCO groups having, sufficient hydrophilic polyurethane compounds in the aqueous phase are formed under CO2 - Cleavage and strong increase in molecular weight of colloidal solutions of predominantly non-crosslinked Polyurethanes.

However, the dispersing process can also be carried out in reverse by initially introducing the aqueous phase and stirring in the polyurethane mass. at This generally less favorable process must be the dispersing process in the Usually aided by an effective high-speed stirrer to get sufficient to get small particles. Spontaneous dispersion occurs only with very hydrophilic ones Polyurethane compounds. It is basically irrelevant whether the salt-forming Acid has been added to the polyurethane composition to be dispersed or to the water. The last-mentioned method is less advantageous because it is carried out batchwise the dispersion medium is depleted of acid and so the dispersing conditions become increasingly unfavorable will. On the other hand, there must be an unnecessarily high acid concentration when the acid is continuously added in purchase be taken. The organic solvent can be used simultaneously or completely or partially removed after the dispersing process, preferably by (vacuum) distillation.

Of course you can also choose different continuous Use working methods. Organic and aqueous phases can be combined in one mixing chamber combine or atomize, also simultaneously or subsequently the solvent Will get removed.

The aqueous solutions and dispersions obtained do not contain any emulsifier stable, but appropriate cationic or neutral emulsifiers and dispersants can be used such as acidic casein, invert soaps, polyvinyl alcohol, oxethylated phenols, oleyl alcohol polyglycol ethers, oxethylated polypropylene glycol or natural products such as gelatine, gum arabic, tragacanth, isinglass. Such additives mainly serve to reduce the relatively high surface tension of the cationic polyurethane dispersions according to the invention. They also influence the chemical stability of the dispersions and the coagulability.

The dispersions can be blended with dispersions of the same charge become, such as B. with polyvinyl acetate, polyethylene, polystyrene, polybutadiene and copoly meri sat plastic dispersions.

Finally, fillers, plasticizers, pigments, hosiery and Silica sols, aluminum, clay, asbestos dispersions incorporated into the dispersion will.

The solutions or dispersions of the polyurethane compositions in organic or aqueous-organic solvents or water can be shipped in a stable manner and can be used for shaping at any later point in time. They dry generally directly to dimensionally stable plastic coatings, but can the shaping of the process products also in the presence of crosslinking agents known per se take place. For this purpose, polyfunctional, substances with a crosslinking effect are added, which after evaporation of the optionally existing solvent at room or elevated temperature chemical crosslinking cause. Sulfur, sulfur brine, formaldehyde and formaldehyde-releasing substances may be mentioned or substances that react like formaldehyde, free and partially or completely blocked polyisocyanates, carbodiimides, polyamines, organic and inorganic peroxides. The possibly dissolved or slurried crosslinkers, fillers, pigments, Blending agents and other additives can be used in the course of the process optionally dissolved or dispersed in an organic solvent or in water Polyurethane compounds are added or added on the mixing roller.

Depending on the chosen chemical composition and the content of Cationic polyurethane plastics are obtained from urethane groups and quaternary ammonium groups with different properties. So can soft sticky masses, thermoplastic and rubber-elastic products of various degrees of hardness up to can be obtained into glass-hard thermosetting plastics. The hydrophilicity of the products can also fluctuate within wide limits. The elastic products can also be used, provided they have not been produced with the addition of crosslinkers, at higher temperatures, for example 100 - 180 0j process thermoplastically. Advantageously, this will be small Amounts of plasticizers or swelling agents, such as. B. polyester, polyether, phthalates, Phosphates, or water added.

The thermoplastic processing can either be carried out directly from the Solvent-containing polyurethane mass go out, which is previously the solvent, e.g. in a kneader or a screw, (partially) withdrawn, or coagulates can be formed z. B. by pressing and drying into thin skins or irregular granules, which are further processed in the usual way. In some cases, aqueous Dispersions can also be sprayed into powders that are sinterable or meltable.

Finally, the products of the process can be used to improve their properties, for example the increase in hydrophilicity and lyophobicity, surface hardness, with aqueous or organic-aqueous solutions of polyvalent anions, e.g. B. Sulphates, Disulfates, phosphates, silicon fluorides, can be post-treated.

The possibility of polyurethane masses of the most varied composition Applying it in a form suitable for the application opens up many new application possibilities. This is how diving articles can be made using the latex foam whipping process Foams, by adding electrolytes to the aqueous solutions and dispersions-coagulates, which, like the solvent-free polyurethane compounds, are processed on the mixing roller can be, and by evaporation of any solvents present tack-free and adhesive films and sheets can be obtained. The process products are for coating or covering and impregnating woven and not woven textiles, leather, paper, wood, metals, ceramics, stone, concrete, bitumen, Hard fiber, straw, glass, porcelain, plastics of all kinds, for antistatic and wrinkle-free finish, as a binder for nonwovens, adhesives, adhesion promoters, Laminating agents, water repellants, plasticizers, binders e.g. B. for cork or wood flour, glass fibers, aabest, paper-like materials, plastic or rubber waste, ceramic materials, as an aid in stuff printing and in the paper industry, as an additive to polymer dispersions, as a layering agent and for leather finishing suitable.

Comparative experiment 1 Procedure according to DAS 1 184 946: 2,500 g of one Polythiomix ethers (70 parts thiodiglycol, 30 parts 1,6-hexanediol; OH number 78) and 5 150 g of tolylene diisocyanate (mixture of isomers 65:35) are at room temperature mixed and reacted for 45 minutes at 80 °. Then one leaves under Cooling at 30 ° a mixture of 1 U00 g butanediol, 1,000 g diethylene glycol and 750 g of N-methyldiethanolamine in 4 liters of technical acetone run in within 30 minutes, with the onset of weak reflux. 30 minutes later the highly viscous mass will be A further 4 liters of acetone were added, which was stirred in homogeneously over the course of 25 minutes will. The solution, which now has a content of 62% polyurethane at a viscosity of 9,500 cP / 25 °, 20 minutes after the homogenization of the solution 96 ccm dimethyl sulfate, 75 g 3, 4-dichlorobenzyl chloride and 51.8 g 1, 3-dimethyl-2, 4-bis-chloromethylbenzene in 0.5 l acetone in the course of 20 minutes at a stirring speed from 100 rpm. added. In contrast to smaller quantities, it works with these Do not stir large amounts of the solution homogeneously, but two form Layers. Even after adding more acetone and increasing the stirring speed to 120 rpm. the crowd remains heterogeneous. A white appears at the interface Layer.

The polyurethane composition is used to prepare a dispersion in large Scale (as opposed to smaller quantities) is often suitable, since even after adding Acetic acid and water do not homogenize.

Comparative experiment 2J mode of operation according to DAS 1 184 946: One proceeds as in comparative experiment 1, but the quaternizing agent mixture in 4, 5 Ltr. Acetone too. First of all, two layers are created, which do not differ at 50 rpm Mix. When increasing the stirrer speed to 100 rpm. occurs in the course of 20 Mix in for a few minutes, during which time strong, layered, silvery-white turbidity occurs Then 3> 5 liters of acetone are added. After an hour of stirring is one white inhomogeneous, highly viscous mass emerged, which after the addition of acetic acid can be converted into an aqueous dispersion.

If the experiment is repeated, 30 minutes after addition of the quaternizing agent behave an almost homogeneous solution, in which, however, the subsequently added 3.5 5 liters of acetone cannot be incorporated homogeneously. The attempt is at These large quantities are difficult to reproduce because of the stirrer shape and speed Too much influence the mixing and thus the course of the reaction.

Comparative experiment 3 Method of operation according to DAS 1 184 946: One proceeds as in comparative experiment 1, but the 62 9Fige polyurethane solution is already diluted at a viscosity of 6,000 cP / 250 with acetone to 45 °. Then one leaves React until the viscosity is constant (8,000 cP / 25 °). That of NCO groups completely Free polyurethane solution is now a solution of 96 ccm dimethyl sulfate, 75 g 3,4-dichlorobenzyl chloride and 51.8 g 1,3-dimethyl-2,4-bis-chloromethylbenzene in 0.5 liters of acetone added at room temperature. Then it is heated to 500. With these large amounts there is no homogeneous mixing, rather than forming silvery-white layers.

After a reaction time of one hour, 230 cc of glacial acetic acid and 77 cc 85 shows phosphoric acid in 614 cc of water, then 30 cc of tristhyl phosphate and stirred in 15.3 3 liters of water. After the acetone has been distilled off, one is obtained relatively coarsely dispersed latex that dries to form hard, glossy coatings.

Example 1: 2,500 g of a polythio mixture ether (70 parts of thiodiglycol, 30 parts of hexanediol-1.6; OH number 78) and 5,150 g of tolylene diisocyanate (mixture of isomers 65: 35) are in the 40 ltr. -V2A kettle mixed at room temperature and 45 minutes reacted at 800. A mixture is then left at 300 with cooling from 1,000 g of butanediol-1,4, 1,000 g of diethylene glycol and 750 g of N-methyl-diethanolamine run in 8 liters of technical acetone within 40 minutes, with weaker Reflux begins. The solution, which has a content of 62% of polyurethane at a Has a viscosity of 4,000 cP / 25 °, 96 ccm of dimethyl sulfate, 75 g of 3,4-dichlorobenzyl chloride and 51.8 g of 1> 3-dimethyl-2,4-bis-chloromethylbenzene in 0.5 liters of acetone within ten minutes at a speed of 30 rpm. added. The solution is stirred in completely homogeneously. Then 3.5 liters of acetone are added and Stirred until a viscosity of 12,000 cP / 25 ° is reached. Meanwhile the polyurethane solution gradually takes on a silvery-white appearance and is with no further dilution of acetone. However, the solution remains uniformly homogeneous and easy to stir.

After a reaction time of one hour, 230 cc of glacial acetic acid and 77 cc 85% phosphoric acid in 614 cc of water, then 3QO cc of triethyl phosphate and stirred in 15.3 3 liters of water. After the acetone has been distilled off receives a very finely dispersed latex is dried on the hard, high-gloss coatings. Pigmented films also have a good gloss.

Examples (B) 2-4 and comparative experiments (V) 4-11: General Production method: 130 g of a polythio mixture ether (70 parts of thiodiglycol, 30 parts of thiodiglycol). 1,6-hexanediol; OH number 78) and 266 »4 g of toluene diisocyanate (mixture of isomers 65: 35) are mixed and reacted at 800 for 30 minutes. To the reaction mixture are successively 160 ccm of acetone, 52 g of diethylene glycol, 52 g of 1,4-butanediol and 39 g of N-methyl-diethanolamine are added to 256 cc of acetone. The solution of the quaternizing agent in 15 ccm acetone is in comparative experiment 4 - 7 at the same time with the methyl diethanolamine solution, for example 2 - 4 25 minutes later at a viscosity of 5 100 cP at 560 (corresponding to 16,000 cP at 20 °) was added to the 62% solution and then 420 ccm of acetone added, while in comparative experiment 8-11 after 25 minutes with 420 ccm of acetone is diluted and 100 minutes later the fully reacted polyurethane solution the quaternizing agent in 100 cc of acetone are added. After 100 minutes (in comparison experiment 8-11 after 60 minutes) the homogeneous or hete @@ genen Solution 6.75 g of phosphoric acid and 5.5 g of triethyl phosphate in 32 g of water, then 680 cc of water were added. The acetone is then distilled off. The resulting Latices, if available, are compared. ed dimethyl sulfate 1, 3-dimethyl-4, 6- N <+) method result or r CE C CQO, pk% TI - E kC 'E vrsuch (V) ccm g V 4 2, 56 Os 07 7> 1 0> 09 0, 16 Quaternizing agent solution clear even still touchable V5 5> 12 0> 14 7> 1 0> 09 0.23 simultaneously with N solution cloudy rapidly C; 1 highly viscous not V 6 ------- 7.1 0> 09 Q30 Methyl diethanolamine more with acetone dilutable V 7 8> 44 0.23 - - 0.23 add quickly cross-linked B 2 2, 56 0> 07 7, 10, 09 0, 16 Quaternizing agent solution clear, after then gradually adding N-N acetone B 3 5, 12 0, 14 7, 1 0, 09 0, 23. Blurring kk Q, ka, O <D low viscosity B 4 7.68 0.21 7.1 0.09 0.30 add k m'ft ba dilutable V8 2> 56 0> 07 7, 1 0, 09 0>'16 Quaternizing agent <C Quaternizing agent in the cloudy solution still V 9 5, 12 0> 14 7> 1 0> 09 0, 23 to the fully reacted stirrable 0000 000 according to Ouaternierungsmfttel V 10 7, 68 0> 21 7, 1 0> 09 0a 30 dissolved polyurethane mass adding white>heterogeneous> ; D no homogenization possible V 11 8.44 0> 23 - - 0a23 retrospectively O) QJQ) lich Latex transfer through properties of latex phosphoric acid (85 %) Triethyl phosphate in water water V 4 6.75 g 5.5 g 32 ccm after adding 300 ccm water quark-like cross-linked mass V 5 - - - latex cannot be produced V 6 - - - latex cannot be produced V 7 - - - latex cannot be produced B 2 6.75 g 5.5 g 32 ccm 680 finely dispersed latex B 3 6.75 g 5.5 g 32 ccm 680 finely dispersed opaque latex B 4 6.75 g 5.5 g 32 ccm 680 finely dispersed opaque latex V 8 6.75 g 5.5 g 32 ccm 680 Coarsely dispersed latex as Example 2 C 9 6.75 g 5.5 g 32 ccm 680 coarse latex, settled V 10 6.75 g 5.5 g 32 ccm 680 coarsely dispersed latex as example 4 V 11 - - - - - - example 5: 15 kg of an adipic acid-phthalic acid-ethylene glycol polyester (OH number 64; molar ratio 1: 1: 2) and 4035 g of tolylene diisocyanate (mixture of isomers 65:35) become 90 Heated to 117 - 120 ° for minutes. The melt is cooled to 700, with 936 Ltr. Diluted acetone, then with 1.5 kg of N-methyl-diethanolamine and 8.22 liters of acetone offset. One hour later a viscosity of 1-800 cP / 250 is reached (solids content 60%). 457.5 g of 1,3-dimethyl-4,6-bis-chloromethylbenzene are added in 2> 7 liters. Acetone, then 7.5 liters of acetone. After 70 minutes the viscosity is 2,000 cP / 250. 30 g of dibutylamine in 300 cc of acetone are added and ten minutes later 305.5 ccm 85 shows phosphoric acid and 19 ccm triethyl phosphate in 1.8 8 liters of water and then add 26 liters of water within 20 minutes. Then the organic Solvent distilled off in vacuo. A 48%, highly viscous, opaque, very fine-grained latex that dries to form high-gloss, flexible coatings.

Example 6: The procedure is as in Example 5, but the organic Polyurethane solution after the addition of dibutylamine with stirring in a solution of 800 cc of glacial acetic acid in 27 liters of water. After distilling off the organic solvent an extremely finely divided opaque latex with a particle size is obtained under 50 m.

Example 7: 500 g of polypropylene ether glycol (OH number 300) are used in 40 ° with 444 g of toluene diisocyanate, whereupon the temperature rises to 850.

It is kept at this temperature for one hour, cooled to 300 and add 6Q g of diethylene glycol and 60 g of N-methyldiethanolamine in 360 cc of acetone. 35 Minutes after the start of the addition, the 81% solution has a viscosity of 5,200 cP / 25 °. 360 cc of acetone are added, whereupon after 30 minutes the now 67% solution has a viscosity of 6,000 cP / 25 °. Then 8.84 84 g of 1,3-dimethyl-4, 6-bis-chloromethylbenzene in 50 com acetone and then 435 cc acetone were added. Man lets react for 90 minutes and then sets 14.14 14 ccm phosphoric acid (85%) in 60 cc water, then 1.4 liters of water. After the acetone has been distilled off a 50% finely dispersed opaque latex is obtained, the hard, high-gloss latex Coatings dries up.

Example 8: 125 g of polypropylene ether glycol (OH number 56) are mixed with 52.5 g of 4,4'-diphenylmethane diisocyanate and 63 g of tolylene diisocyanate (mixture of isomers 65:35) stirred at 800 for 30 minutes. The reaction mixture is at 60 ° 100 ccm Acetone (water content 0.24%) and at 300 30 g of N-methyldiethanolamine and 24 g of diethylene glycol in 100 cc of acetone added within 30 minutes. Immediately afterwards, the low viscosity 65% own solution 7.82 ccm dimethyl sulfate and 7.05 g 1,3-dimethyl-4,6-bis-chloromethyl-benzene in 37 cc acetone were added. After 30 The quaternized, still free NCO groups are stirred for minutes at 60 ° Polyurethane mass with slow stirring a solution of 23.5 g of glacial acetic acid in 750 ccm Water added. An almost clear aqueous-organic polyurethane solution is obtained, from which the acetone is removed by distillation.

A slightly opaque, purely aqueous, colloidal solution results.

The solution is ideal for surface sizing of paper, which it gives a very low water absorption capacity.

Example 9: The procedure is as in Example 8, but with moderate Stir the quaternized polyurethane solution of the solution of 23.5 g of glacial acetic acid in 750 cc of water. The colloid-aqueous polyurethane solution obtained after the acetone has been distilled off does not differ from that obtained in Example 8.

Example 10: The procedure is as in Example 8, but using of 58 g of 4,4'-diphenylmethane diisocyanate and 63 g of tolylene diisocyanate. The received Colloid-aqueous polyurethane solution is more viscous and highly opaque, i.e. more coarsely dispersed than that obtained in Example 8. It is also very suitable for paper sizing.

Example 11: The procedure is as in Example 8, but using of 78 g of 4,4-diphenylmethane diisocyanate and 63 g of tolylene diisocyanate. During the When water is added, the high molecular weight polyurethane is formed with the development of C02.

A colloidal viscous 36 shows polyurethane solution which both Very well suited for surface sizing as well as for the mass sizing of paper is. The product can also be used to produce high-gloss, waterproof covers suitable.

Example 12: The procedure is as in Example 10, but using of 20.5 5 g of 1,4-butanediol instead of diethylene glycol. The product results in the paper sizing results are even better than those obtained according to Example 10.

When using 23.7 g neopentyl glycol instead of 1,4-butanediol an opaque aqueous polyurethane solution will also behave with its 3-sizing properties are a little less good.

Example 13: 130 g of a polythio mixed ether (70 parts of thiodiglycol, 30 parts 1,6-hexanediol, OH number 78) and 266.4 g tolylene diisocyanate (mixture of isomers 65:35) are mixed and reacted at 800 for 30 minutes. To the reaction mixture 100 ccm of acetone, 52 g of diethylene glycol, 52 g Butanediol-1, 4 and 39 g of N-methyldiethynolamine in 256 g of acetone were added. After 25 Minutes are 6 g of phosphoric acid in 15 ml of acetone and then 313 cc of acetone added. The cloudy solution is stirred for two more hours at 50 °, the viscosity continues to increase.

The viscous solution initially becomes clear when water is added, after 300 ccm it is cloudy again and begins to become inhomogeneous. After adding 15 cc of acetic acid a further 400 ccm of water are stirred in, creating a milky-white latex, which is freed from the solvent by distillation. When drying on glass plates shiny, water- and solvent-resistant, flame-retardant coatings are obtained.

Example 14: Example 13 is replaced with 10 g of chloroacetic acid Phosphoric acid carried out. -After 200 ccm of water have been stirred in homogeneously, after adding 20 ccm of acetic acid, a further 400 ccm of water can be stirred in, whereby a milky-white latex is formed, which is produced by distillation from the solvent is released. When drying on glass plates, glossy coatings are obtained.

Claims (1)

Claim; Process for the production of polyurethane -I (plastics, including sheet-like structures or adhesion promoters based on the diisocyanate polyaddition process with a content of 0.22 - 2% quaternary ammonium groups on the basis of compounds with reactive hydrogen atoms with a molecular weight from 300 - 20,000, polyisocyanates and chain extenders with at least two reactive hydrogen atoms, with at least one chain extender at least a) one tertiary basic nitrogen atom or b) at least one reactive one Contains halogen atom or a -5Ö2-O-R group, as well as in case a) alkylating agents and / or acids or in case b) tertiary amines and solvents, characterized in that that there is so much of the alkylating agent (s) and / or acids or the tertiary amine while between the polyhydroxyl compounds, polyisocyanates and chain extenders reaction taking place immediately after combining at least 80% of the remainder Reactant admits, “as long as the viscosity of a 60% own solution is still is below 7,000 cP / 25 that the content of quaternary ammonium groups is at least 0.21% and optionally after further addition of acid and optionally Conversion of the dissolved polyurethane mass into a latex in a manner known per se or an aqueous colloidal solution at any time the organic or Removed aqueous solvents or dispersants.