DE2855770A1 - Prodn. of mono- and polymeric hydantoin cpds. - from isocyanate and alpha, beta-di:carbonyl cpds. - Google Patents

Abstract

Prepn. of cpds. (I) contg. >=1 hydantoin ring is carried out by reacting organic isocyanates (II) with alpha, beta-dicarbonyl cpds. (III) at -20 to +500 degrees C. Pref. starting materials (III) are of formula R1COCOR2 (where R1 and R2 are H or aliphatic, cycloaliphatic, aliphatic-aromatic, aromatic or heterocyclic gps. opt. substd. by halogen, NO2, -CO-(sic), CN, OH or COR3, where R3 is OH, NH2, alkylamino, dialkylamino, alkoxy, aryloxy H or an aliphatic, cycloaliphatic, aliphatic-aromatic, aromatic or heterocyclic gp., or R1 + R2 can form a cyclic organic gp.). Monomeric hydantoins are useful in the pharmaceutical and plant protection fields; oligomeric and polymeric hydantoins are useful for the mfr. of heat-resistant coatings foils, powder, adhesives, lacquers, fibres and mouldings. The process gives high yields of (I) from readily available starting materials in fewer steps than prior art processes.

Description

Hydantoins

The invention relates to a method for producing condensates with at least one hydantoin or thiohydantoin ring in the molecule by reaction of dicarbonyl compounds and organic isocyanates and their use as biochemical active ingredients or for the production of heat-resistant coating agents and coatings.

Process for the production of hydantoins (e.g. Am.

Chem. J. 45/383 (1911)) or polyhydantoins (e.g. BE 678 282) known and meanwhile in the most diverse variations and embodiments has been described in a wide variety of solvents.

Low molecular weight hydantoins are preferred in the pharmaceutical and crop protection sectors, higher molecular weight hydantoins, for example in the heat-resistant coating middle sector used (French Pat. 1 484 694).

Surprisingly, it has now been found that the reaction of organic isocyanates with O2-bicarbonyl compounds of the general formula: in which R1 and R2, independently of one another, denote hydrogen, an aliphatic radical, a cycloaliphatic radical, an aliphatic-aromatic radical, an aromatic radical, a heterocyclic radical, each of which is optionally accompanied by halogen-, 3 -NO2-, -CO-, - CN, -OH, COR3 groups with R3 = hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy group, hydrogen, an aliphatic, cycloaliphatic, aliphatic-aromatic, aromatic or heterocyclic radical or substituted together as Members of corresponding cyclic organic radicals can be linked to one another, compounds containing hydantoin rings are obtained in good yields at temperatures from -20 to 5000C, preferably from 0 to 4500C.

For each equivalent of the <ß-dicarbonyl compound, at least 2 Val isocyanate are used.

The smooth course of the multi-stage reaction, the also enables the production of polymers, was not to be expected because every stage especially in the presence of excess amounts of isocyanate, to a large number of complicated Mixtures of substances can react. In the context of the implementation according to the invention, preference is given to Any available components are used and thus the mostly numerous preliminary stages the known hydantoin production process avoided.

The reaction according to the invention can be represented formally by the following equation: where the radicals R1 and R2 have the meaning given above, R4 is the optionally substituted aliphatic, cycloaliphatic, aliphatic-aromatic, aromatic or heterocyclic radical of an organic isocyanate and n is an integer of 1-4, preferably 1-3, particularly preferably 2 target.

Per mole of, ß-dicarbonyl compounds should be 2 to 8 eq, preferably 2 - 4 val isocyanate are used, but the course of the reaction is not either disturbed by excess isocyanate.

For n = 1, there are monomolecular hydantoins of the general formula and for n 1, depending on the stoichiometric ratios of the starting materials, oligomeric or polymeric hydantoins with the repeating structural unit of the general formula obtained, where R1, R2 and R4 have the abovementioned formula and z is an integer from 2 to 2000, preferably from 2 to 1000.

If more than i, preferably Used 1.5 to 2.0 mol of a diisocyanate, polyisocyanates are formed with the above anqeqebenen, possibly recurring structural unit, which optionally is linked via R4 radicals, and optionally contains blocked NCO end groups.

The hydantoin isocyanates in this series are available as components and crosslinkers, for example in polyesters, polyethers, polyurethanes, polyhydantoins, polyesterimides, Polyamide-imides and polyimides are suitable.

The hydantoins can be identified by the characteristic IR bands of the hydantoins be identified. The higher molecular weight hydantoins have 30% strength by weight Solutions with, for example, acetophenone, butyrolactone, cresol or alkyl benzoate at 25 ° C., solution viscosities of 50 to 500,000 mPas, preferably from 500 to 200,000 mPas.

Preferred g, ß-dicarbonyl compounds are compounds of the general formula: used, n which preferably R1 and R2 are identical or different hydrogen, an aliphatic radical with C1-C20, a cycloaliphatic radical with C5-C20, an aliphatic-aromatic radical with C7 -C20, an aromatic radical with C6-C20, a heterocyclic radical with 4-15 ring members, each optionally with halogen, -NO2-, -CO-, -CN-, -OH-, -COR3 groups with R3 = hydroxyl, amino, alkylamino, dialkylamino, Alkoxy or aroxy group, hydrogen, an aliphatic radical with C1-C20, cycloaliphatic radical with C5-C20, aliphatic-aromatic radical with C7-C20, an aromatic radical with C6-C20 or heterocyclic radical with 4-16 ring members can be substituted.

The radicals R1 and R2 can, for example, hydrogen, a methane, Ethane, hexane, cyclohexane, propene, benzene, toluene, piperidine, morpholine, Imidazole, formymethyl, alkylcarbonylmethyl or arylcarbonylmethyl, an alkoxycarbonylmethyl, Be aroxycarbonylmethyl radical, etc. and optionally together with up to 8 ring members Form containing ring.

R1 can preferably be an alkyl or aryl radical, which optionally with the radical R2 can form a ring containing up to 8 ring members.

R1 and R2 are particularly preferably aryl radicals.

The following are examples of preferred g, B-dicarbonyl compounds called: Glyoxal, Methylglyoxal, Phenylglyoxal, Diacetyl, Benzil, Cyclohexanedione-1,2, 1, 2-acenaphthylenedione, 9, 10-phenantrendione, ß-naphthalenedione, 1,2-benzoquinone.

Preferably, diacetyl and / or benzil are particularly preferred Benzil is used.

Mono- and / or polyiso (thio) cyanates can be used as organic isocyanates be used.

As monoisocyanates in the context of the invention are aliphatic and aromatic compounds, optionally substituted by heteroatoms, with a NCO group used in the molecule, e.g. alkyl isocyanates such as ethyl, methyl, butyl, Dodecyl and stearyl isocyanate, aromatic, optionally substituted monoisocyanates such as phenyl, tolyl, isopropyl, nonyl isocyanate, nitro, alkoxy, aroxy, chlorine, Dichloro, trichloro, tetrachloro, pentachloro, benzyl, bromophenyl isocyanate or Isocyanatobenzoic acid ester, -phthalic acid ester, -isophthalic acid acid esters, Isocyanatobenzonitrii, cycloaliphatic isocyanates such as cyclohexyl isocyanate and unsaturated isocyanates such as allyl, oleyl, cyclohexenyl isocyanate.

Starting components to be used according to the invention are also available aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic Polyisocyanates into consideration (see. Annalen 562, pages 75 to 136), for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, Cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate and any Mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl-cyclohexane (DAS 1 202 785), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, Polyphenyl-polymethylene-polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation and e.g. in the British patents 874 430 and 848 671, perchlorinated aryl polyisocyanates such as them e.g. in German Auslegeschrift 1 157 601, carbodiimide groups containing polyisocyanates, as described in German Patent 1,092,007 become, diiso- cyanates, as described in U.S. Patent 3,492,330 are described, polyisocyanates containing allophanate groups, such as those described, for example, in British Patent 994 890, Belgian Patent 761 626 and the published Dutch patent application 7 102 524, isocyanurate groups containing polyisocyanates, as e.g.

in German patents 1 022 789, 1 222 067 and 1 027 394 as well as in the German Offenlegungsschriften 1 929 034 and 2 004 048 are, urethane group-containing polyisocyanates, such as those in the Belgian U.S. Patent 752 261 or U.S. Patent 3,394,164, Polyisocyanates containing acylated urea groups according to the German patent 1 230 778, polyisocyanates containing biuret groups, such as those used, for example, in the German Patent 1 101 394, British Patent 889 050 and French No. 7,017,514 are prepared by telomerization reactions Polyisocyanates such as those described in Belgian patent 723 640 polyisocyanates containing ester groups, such as in the British patents 956,474 and 1,072,956, in U.S. Patent 3,567,763 and in German Patent 1,231,688, transesterification products of the above isocyanates with acetals according to German patent specification 1 072 358.

It is also possible to use the technical isocyanate production accruing, Distillation residues containing isocyanate groups, optionally dissolved in one or more of the aforementioned polyisocyanates to be used. It is also possible to use any mixtures of the aforementioned polyisocyanates.

Isocyanates of the general formula R4 (NCO) n are preferably suitable in which R4 stands for one, optionally with halogen, alkyl with C1-C10 and / or aryl groups with C6-C12-substituted alkyl radical with 2 - 20 carbon atoms, an aryl radical with 5 - 12 carbon atoms, a cycloalkyl radical with 5 - 12 carbon atoms, an alkyl aryl radical with 6-20 carbon atoms and an aryl or cycloalkyl radical containing heteroatoms such as N, 0 or S with 5 - 12 carbon atoms. n is an integer from 1 to 4, preferably 1 to 3, particularly preferred 2. Aliphatic radicals with 2 to 12 carbon atoms are particularly preferred or aryl radicals such as phenyl, tolyl, naphthyl, diphenylmethane and diphenyl ether radicals.

The technically easily accessible mixtures are preferably used from tolylene diisocyanates, m-phenylene diisocyanate, and phosgenated condensates from aniline and formaldehyde with polyphenylene-methylene structure and the symmetrical ones Connections 4,4'- Diisocyanatodiphenylmethane, 4,4'-diisocyanatodiphenyl ether, p-phenylene diisocyanate and 4,4'-diisocyanatodiphenyldimethyl methane and isophorone diisocyanate and hexamethylene diisocyanate.

The isocyanates can be in free form, furthermore partially or completely also in the form of their compounds containing reactive hydrogen upon reaction accessible and reacting as isocyanate releasers under the reaction conditions Derivatives are used.

The adducts of lactams, oximes and CH-acidic compounds as well as the carbamic acid esters obtained from aliphatic and aromatic mono- and polyhydroxy compounds, for example of the general formula, are preferably used as breakers used, where R4 and n have the meaning given above and M is the organic radical of a monohydroxy compound and Q is the organic radical of a bis- or trisfunctional hydroxy compound, preferably M and Q, identical or different, an aliphatic radical having 1-10 carbon atoms , a cycloaliphatic radical with 5 - 12 carbon atoms, an aliphatic-aromatic radical with 7 - 12 carbon atoms and / or an aromatic radical with 6 - 12 carbon atoms, each with alkyl with C1-C10 and / or aryl groups can be substituted by C6-C12, and y is an integer from 1 to 1000, preferably from 1 to 100.

Examples are the carbamic acid esters from phenol, isomeric cresols, their technical mixtures and similar aromatic hydroxyl compounds, aliphatic Monoalcohol. such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Cyclohexanol, allyl alcohol, benzyl alcohol and aliphatic diols or polyols such as ethylene glycol and trimethylol propane, glycerin and / or trishydroxyalkyl isocyanurates, etc., further the addition products with pyrrolidone (2), caprolactam, butanone oxime, malonic ester, Acetoacetic ester and acetophenone listed.

The isocyanate releasers can be used as such or only in situ can be generated by reaction with the appropriate reactants.

Instead of the (poly) isocyanates mentioned, it is also possible to use the analogous (Poly) isothiocyanates can be used as starting materials.

According to the invention, particularly as a blocking agent as well as a solvent preferred hydroxyl alkyl ethers are, for example, compounds of the general formula R5- (oR6) -OH, q in R5 is an optionally substituted aliphatic radical with C1-C20, preferably C1-C8, cycloaliphatic radical with C5-C18, preferably CS -C8, aliphatic-aromatic Radical with C7-C16 or aromatic radical with C6-C14, e.g. with alkoxy, aroxy or hydroxyl groups can be substituted, an aliphatic radical with 2 - 20 C atoms and q is an integer from 1 to 100, preferably 1 to 4. Preferably those hydroxyalkyl ethers are used according to the invention which have one per molecule ydroxy group and in which R6 is a radical with two carbon atoms in the chain, which may, for example, be substituted by alkyl groups is, e.g. the methyl, isopropyl, cyclohexyl, benzyl, phenyl and methoxy ethyl-ethylene glycol and propylene glycol or diethylene glycol and dipropylene glycol monoether.

The inventive conversion of the g, ß-dicarbonyl compounds with the organic isocyanates to the compounds containing hydantoin groups can be used in Solvents which do not react under the reaction conditions or which are loose, Forming further reacting addition compounds or in bulk or in an excess one of the reaction components can be carried out.

In addition to the blocking agents listed, solvents are also suitable also hydrocarbons, halogenated hydrocarbons, alcohols, esters, cyc- tab Esters, ketones, ethers, substituted amides, nitriles; Examples are xylenes, o-dichlorobenzene, benzyl alcohol, phenoxyethanol, acetophenone, cyclohexanone, ethylene glycol butyl ether, Diethylene glycol methyl ether, propylene carbonate, Q-caprolactam, dimethyl sulfoxide, glycol monomethyl ether acetate, ; 24-butyrolactone, ε-caprolactone, benzoic acid alkyl ester, N-methylpyrrolidone, dimethylformamide, Dimethylacetamide, benzonitrile and others as well as their mixtures.

Aliphatic and aromatic hydrocarbons are also used as co-solvents such as cyclohexane, xylene, toluene and their technical mixtures such as Solvesso 100 and Suitable for sovent naphtha.

However, it does not have to be a solvent, if necessary stoichiometric Blocking agent amounts are used.

To carry out the process according to the invention, the reaction components are with or without a solvent and / or blocking agent, a few minutes to several Hours at temperatures from -200C to 5000C, preferably OOC to 4500C, held. The course of the reaction can be followed via the evolution of gas and the IR spectra.

The acidity of acidic solvents such as phenols or cresols can lead to shortened reaction times as part of the response process. In inert media or in melts, for example, carboxylic acids with sufficient melting or boiling point such as acetic acid, benzoic acid, succinic acid, benzene dicarboxylic acids, Butanetetracarboxylic acid, trimellitic acid or

their anhydrides, if appropriate, also as catalysts that can be installed in amounts from 0.1 to 40, preferably from 1 to 10 percent in Val, based on a val isocyanate, can also be used.

To accelerate the ongoing reactions are those from isocyanate chemistry known catalysts such as bases, for example triethylamine, N-methylmorpholine, Endoethylene piperazine, such as acids, for example p-toluenesulfonic acid, such as metals, in particular of iron, sliding zinc, tin, copper, cobal, titanium, manganese, for example Titanium tetrabutylate, titanium amino alcohol, iron acetylacetonate, dibutyltin laurate, lead acetate, Zinc octoate or phosphorus compounds such as trialkylphosphine to be used.

It is sometimes advantageous to carry out the reaction in several stages. Through gradual temperature control and / or through gradual or gradual Addition, if appropriate, of different isocyanates or isocyanate mixtures can be one defined structure of the process products according to the invention can be achieved.

For example, in a first stage, optionally in one Solvents and / or blocking agents, an adduct or condensate are produced that then at a higher temperature, possibly with evaporation of the solvent, if appropriate after the addition of blocking agents with cyclization and / or chain extension and / or networking in the possibly high molecular weight condensation product transforms. If this is then used for coating, it can also be made from melts or aqueous systems or as a powder.

Sometimes the reaction is expediently under an inert Protective gas such as N2 or argon carried out.

Finally, the reaction according to the invention can be carried out continuously or discontinuous execution or optionally in autoclaves under pressure take place for the purpose of a higher reaction temperature.

In general, according to the reaction according to the invention advantageously at least 2 to 8 eq per mole of the g ß-dicarbonyl compound, preferably 2 to 4 val isocyanate used.

The work-up of the low molecular weight reaction products can after common methods such as crystallization.

Another embodiment of the reaction according to the invention consists in that optionally in situ, for example, water, mono- and / or polyvalent amines, mono- and / or polyvalent ureas, mono- and / or polyvalent ureas valuable Alcohols, for example tertiary butanol, diacetone alcohol, ethylene glycol, dipropylene glycol, Trimethylolpropane, glycerine, trishydroxyethyl isocyanurate and / or the combination from cyanuric acid triaryl esters and polyols and / or optionally polybasic carboxylic acids and / or their esters and / or their anhydrides, for example based on those mentioned Polyearboxylic acids, preferably phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Pyromellitic acid, butanetetracarboxylic acid, etc., and / or polyfunctional, preferably bis-functional α α-aminocarboxylic acid derivatives according to the Belgian U.S. Patent 678,282 or U.S. Patent 3,397,253 and / or other polyisocyanates or polyisocyanate splitters, or those enbfleedh = dea polyamines and possibly with the addition of auxiliaries and additives such as -CaproLRam, # -caprolactone, etc. used and in a flexible manner to linear and / or branched plastics with e.g. hydantoin, Ester, carbamide ester, amide and / or imide groups of good solubility, higher Temperature resistance, good elasticity and good heat shock behavior implemented can be.

In a special variant of the method according to the invention polymeric and / or incorporated into polymers and / or linked to polymers o6, ß-dicarbonyl compounds with the optionally blocked organic isocyanates to give hydantoin groups Connections implemented.

Of course, the condensation products according to the invention, possibly also their preliminary stages, Polyesters, preferably hydroxyl groups containing polyesters, e.g. preferably from maleic anhydride, phthalic anhydride and / or maleic acid, fumaric acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, Trimellitic acid and / or trimellitic anhydride and / or their esters, ethylene glycol, Dipropylene glycol, glycerine, trimethylol propane and / or trishydroxyethyl isocyanurate and / or the combination of cyanuric acid triaryl esters and polyols, polyethers, for example from ethylene oxide and / or bis (hydroxyphenyl) propane and epichlorohydrin, Polyurethanes, polyamides, polyolefins, polyacetates, polyepoxides, polyimides, Polyamide-imides, polyester-imides, polyesters, polyester-animides, polyimino-polyesters, Polyimide isocyanates, polyhydantoins, polyhydantoin isocyanates, etc. mixed in and optionally condensed on and / or in or the reaction according to the invention in The presence of these components can be carried out. In all cases this arises modified polymers which, in addition to the (thio) hydantoin rings, may contain additional Ether, carsmid ester, carboxylic acid ester, caixic acid amide, imide, ester amide, -esterimide-, -amidimid- and / or -esteramidimidgruppierungen contain.

The proportions of these additives can be used within wide limits fluctuate, preferably with regard to the condensate according to the invention 10 - 500 tonnes by weight are used.

The isocyanates can also be used in pure form or as technical reaction products be used. One further embodiment of the invention Process claims the use of any isocyanate mixtures, which means, for example other organic isocyanates can be used in any sub-steps can.

In the context of the process according to the invention, products with optionally blocked isocyanate groups are formed. Mix by using isocyanate, for example from poly- and monofunctional isocyanates is the degree of polymerization and to control isocyanate content of the reaction according to the invention. Accordingly, products can with a comparable degree of polymerization, but lower, possibly blocked Isocyanate content produced by using calculated proportions of monoisocyanates will. For example, phenyl isocyanate, naphthyl isocyanate, isocyanatobenzoic acid ester, Isocyanatoacetic acid esters, etc.

The low resp. monomolecular hydantoins have biochemical effects according to the invention Polyhdantoine has a special temperature resistance and good solubility also in preferably environmentally friendly solvents.

The plastics modified with the polycondensates according to the invention also show improved temperature behavior. The polymers can be used to manufacture temperature-resistant glue, varnish, foils, fibers, powder and plastic fabrics as well as for coating heat-resistant substrates. Your properties can, depending on the area of application, by adding fillers, pigments, low and high molecular weight components such as polyurethanes, polyesters, polyesterimides, polyimides, Polyamide imides, polyamides, polyester amide imides, polyvinyl acetate, epoxies, polycyanates, Silicone resins, can be varied within wide limits.

The products containing hydantoin groups are preferred for stoving enamels, especially wire or

Electrical insulating varnish suitable. These paint binders come in the abovementioned solvents or solvent mixtures are used, which according to the invention additionally a certain proportion of nonsolvents or

Co-solvents can be added. These blending agents are aliphatic, preferably aromatic, hydrocarbons, optionally also lower ones Alcohols, for example cyclohexane, toluene, xylene, technical mixtures thereof such as Solvesso and solvent naphtha, as well as ethanol, butanol, amino alcohol, etc.

The solids content of the possible paint solutions can vary within wide limits and depends on the dissolving behavior of the binder, but also on the intended use certainly. The solids content is preferably in the range from 20 to 70% by weight. The polyhydantoins according to the invention are themselves preferably phenol-free Solvents have sufficient solubility and can be used on conventional painting machines as well as impregnating varnishes with contents of up to 60% (if necessary also from the pure Melt or powder).

Finally, the curing reaction of the coating agent also occurs accelerated by adding the above-mentioned catalysts, i.e. the reaction time is shortened or the baking temperature is lowered at the same time. So is Complete curing even on particularly fast-running wire enamelling machines to achieve the paint film.

Example 1 210.2 g of benzil are at room temperature under N2 with 238.2 g phenyl isocyanate and 0.2 g tert-butanol mixed and approx. 7 hours at approx. 1750C Stirred until about 1 molar equivalent of CO is developed or until NCO has been consumed.

A total of 360 g of a TLC-uniform product with a softening point of approx. 1860C isolated will.

The compound shows the bands typical for hydantoins in the IR spectrum at 1720 and 1780 cm 1. According to the NMR spectrum and the elemental analysis: C27 80.2% H20 5.0% N2 6.9% 02 7.9% found: 80.4 / 80.5 5.0 / 5.3 6.7 / 6.9 it is around 1,3,5,5-tetraphenylhydantoin.

Example 2 210.2 g of benzil are converted into 500 at room temperature under N2 g of m-cresol homogenized, with 250.2 g of 4,4'-diisocyanatodiphenylmethane and 0.5 g N, N'-dimethylurea and 20 g xylene are added and the mixture is slowly heated to about 2000C. In approx. 12 hours approx. 1 molar equiva- lent C02 developed resp. all NCO groups have been consumed.

With increasing viscosity, a total of 575 g is added in portions m-cresol is finally diluted to a solution of approximately 30% by weight. One homogenizes another 1 hour at 2000C.

The approx. 30 dough lacquer solution has a viscosity of 4 700 cP20 ° C. The binder remaining after a methanol precipitation has the in the IR spectrum the hydantoins own gangs.

D3r 0.7 mm enamelled Cu wire produced in a 4 m furnace at 10 m per minute has been tested according to DIN 46 453 and has a softening temperature of at least 3300C, a heat shock of at least 2600C, a permanent heat resistance of at least 21 days at 2000C, a paint film hardness of at least 5H and a good one Chemical resistance.

Example 3 231.2 g of benzil are at room temperature under N2 with 217.7 g of a mixture of 80% 2,4- and 20% 2,6-tolylene diisocyanate mixed, homogenized and after adding 0.5 g of 4,4'-diaminodiphenylmethane to approx. 2000C in approx. 2 hours heated. The condensation is carried out for about 7 hours at about 2000C to a total of one equivalent CO2 was created.

With increasing viscosity, a total of 650 g is added in portions t -butyrolactone added. Finally, a total of 43.3 g of benzyl alcohol are added and homogenized again for 1 hour at 2000 to 2050C.

The approx. 40% oligohydantoin solution has a viscosity of approx. 9,700 cP20 ° C.

It is with 827 g of benzyl alcohol, 534 g of methyl benzoate and 267 g of propylene carbonate and diluted with 1085 g of a polyester made of 4.0 mol of dimethyl terephthalate, 0.8 mol of trimellitic anhydride, 0.9 mol of terephthalic acid, 2.0 mol of tris (2-hydroxyethyl) isocyanurate, 0.5 moles of glycerin, 7.0 moles of ethylene glycol, 200 g of Solvesso, 3.0 g of lead acetate and 1.0 g of butyl titanate with a hydroxyl group content of approx. 4.5% by weight are added.

The mixture is homogenized for 1 hour at 180 ° to 2000 ° C., then added at 1000C to 800C the solution of 15 g of titanium tetrabutylate in 30 g of acetylacetonate added and stirred for about 1 hour at 800 to 700C.

The viscosity of the approx. 40% paint solution is 2310 cP200C.

The copper wires coated with it in a 4 m furnace at 10 m per minute 0.7 mm in diameter have a softening temperature of at least 3300C, a heat shock of at least 260 ° C and a permanent heat resistance at 2000C of at least 14 days and good chemical resistance.

Example 4 57.6 g trimellitic anhydride and 8.3 g isophthalic acid are mixed under N2 with 150 g of t-butyrolactone and 200 g of toluene, then with 157.7 g of benzil and then from 300 to 40 ° C. with 350.3 g of 4,4'-diisocyanatodiphenylmethane and stirred up 0.5 g of endoethylene piperazine.

The mixture is stirred for about 4 hours at room temperature, then added approx. 500C with 200 g of dimethyl terephthalate, 96.1 g of trimellitic anhydride and 0.5 g of endoethylene piperazine, homogenized, then heats with discharge, if necessary below 200 torr, from CO2, ethanol, toluene, etc.

in steps above 1200C, 1500 1700C to 1900C.

A total of approx. 1 hour at 190 ° C, approx. 3 hours at 2050 up to 2100C and approx. 2 hours at 2100-2150C or until the end of CO2 / alcohol development condensed.

Then the mixture is at about 1700C with 532.1 g dimethyl terephthalate, 83.1 g terephthalic acid, 326.6 g trimellitic anhydride, 168.5 g 4,4'-diaminodiphenylmethane, 734.1 g tris (2-hydroxyethyl) isocyanurate, 3.0 g lead acetate, 1.0 g butyl titanate and 50 g xylene are added, homogenized and then in approx.

6 hours over 1700C at 2000 to 2200C until condensed until none Distillate passes below 150 0C more.

Finally, 186 g of ethylene glycol and 46 are added at 1700C g glycerine, condensed again at 2000-2200C until no more distillate below 1500C accrues and then condenses at 2100-2300C initially directly, finally below approx. 200 Torr until the resin thinned to approx. 50% with? £ -butyrolactone has reached a viscosity of approx. 11,000 cP20 ° C.

For the wire enamelling test, the approach was at 150 ° to 1200C with 1000 g t -butyrolactone, 1386 g benzyl alcohol diluted with the solution of 12.5 g titanium tetrabutylate added in 25 g of acetylacetone and homogenized for about 1 hour at 1200 to 1000C.

The approx. 50% lacquer solution has a viscosity of 11 350 cP200C.

The resulting after appropriate dilution to approx. 2000 cP20oc in one 0.7 mm enamelled Cu wire produced in a 4 m furnace at 10 m per minute was made according to DIN 46 453 checked.

It has a softening temperature of at least 3300C, a Heat shock of at least 2600C, a permanent heat resistance of at least 14 Days at 200 ° C, a scraping resistance of at least 90 double rubs, a film hardness of at least 5 H, a dielectric strength of at least 9 KV and a good one Chemical resistance.

Furthermore, with the undiluted binder in per se known Way, with the help of extrusion technology, appropriately pretreated Cu wires from 0.7 mm can be coated. Your test according to DIN 46 453 results even at clearly increased take-off speeds the level of values listed above.

On the other hand, the above undiluted binder can be used directly in the pulverized known manner and as such, for example, on Erichsen sheets be applied. The one after tempering for 15 minutes at 2500C and 10 minutes The paint film obtained at 3000C also has the good qualities already mentioned above mechanical and electrical properties, especially high heat resistance with a melting point above 3500C.

Example 5 105.1 g of benzil and 199.2 grams of N, N'-bis (2-methoxycarbonylpropyl) -4,4'-diaminodiphenylmethane are dissolved under N2 at approx. 300C in 500 g m-cresol, from 350-400C with the solution 250.2 g of 4,4§-diisocyanatodiphenylmethane in 200 g of toluene are added, approx. 2 hours stirred and mixed with 0.5 g of endoethylene piperazine. Then you heat over 1500-1700C with removal of toluene, ethanol, CO2 to approx. 2000C, holds approx. 3 hours at 200 ° - 2050C and another approx.

3 hours at 2050-2100C.

In the course of increasing viscosity, it must be added in portions with a total of 667.8 g of phenol diluted and then added for approx. 1 hour at 2000C will.

The approx. 30% polyhydantoin solution has a viscosity of approx. 117,500 cP20 ° C.

One coated with this Laidßsung in the heat and at 2500C during 15 minutes and at 3000C for 10 minutes stoved Erichsen sheet is obtained a paint film of good elasticity, adhesive strength and chemical resistance as well as a pencil hardness of 5 H.

One produced from this lacquer, e.g. on glass, in the known manner Film has good mechanical properties, high heat resistance and a Melting point of at least 3800C.

Claims (5)

Process for the production of at least one hydantoin ring containing compounds, characterized in that one organic isocyanates with i, ß-dicarbonyl compounds at temperatures from -20 to 5000C. 2. The method according to claim 1, characterized in that the Q, ß-dicarbonyl compounds are compounds of the general formula are used, in which R1 and R2, identically or differently, denote hydrogen, an aliphatic radical, a cycloaliphatic radical, an aliphatic-aromatic radical, an aromatic radical, a heterocyclic radical, each of which is optionally accompanied by halogen-, -NO2-, - CO, -CN, -OH, COR3 groups with R = hydroxyl, amino, alkylamino, dialkylamino, alkoxy or aroxy group, hydrogen, an aliphatic, cycloaliphatic, aliphatic-aromatic, aromatic or heterocyclic radical substituted or they can also be linked together as members of corresponding cyclic organic radicals. 3. The method according to claims 1 and 2, characterized in that that the 9, ß-dicarbonyl compounds before, during or after their conversion with organic Isocyanates with polycarboxylic acids, their anhydrides and / or esters and / or polyols and / or amines and / or tertiary alcohols and / or water and / or polyfunctional α-aminocarboxylic acid derivatives are mixed and reacted. 4. Products containing hydantoins and / or hydantoin rings according to the The method of claims 1 to 3. 5. Use of the polyhydantoins obtained according to claims 1 to 3 undior hydantoin rings-containing condensates for the production of heat-resistant Coating materials, foils, powders, adhesives, lacquers, fibers, moldings.