DE2264265A1 - Poly-4-(thio) imidazolin-2-ones - prepd. by condensing acyloins and polyamines and reacting alpha-aminoketones obtd. with polyiso (thio) cyanates - Google Patents

Abstract

Poly-4-imidazolin-2-ones (I) or -4-thioimidazolin-2-ones (II) (where in (I) X = -O- and in (II) is -S-; n is 15-10000 (20-500) R1 and R2 denote H, 1-6 (1-4)C aliphatic, 5-12 (6) C cycloaliphatic, 5-12 C aryl opt. substd. by 1-4C alkyl or halogen, or 7-10C alkylaryl or aralkyl gps. R3 and R4 are 2-10 (2-6)C aliphatic, 5-12 (6) C cycloaliphatic, 5-12C aryl opt. substd. by 1-4C alkyl, halogen, -CN, alkoxy or -NO2, 7-10C alkylaryl or R5-Y-R6, in which -Y- is -S-, -O-, -SO2-, -CO- -CH2-, Me-C-Me, -O-(CH2)2-4-O-, and R5 and R6 are 2-6C aliphatic, 5-12C aryl or cycloaliphatic gps) are useful for mfr. of heat-proof plastics. as filaments, foils, moulded articles and lacquers, e.g. stoving lacquers.

Description

Poly-4-imidazolin-2-ones The invention relates to a method for Production of new poly-4-imidazolin-2-ones (I) or poly-4-thioimidazolin-2-ones (II) by reacting acyloins, polyamines and polyisocyanates or polyiso (thio) cyanates.

In DOS 1 935 279, polyimidazolinones, in which the monomer units linked by carbon atoms, and a process for their production is described, by combining aromatic polyacyloins with ureas or thioureas to give 4,5-aromatic substituted Polyimidazolinpnen implemented.

It is the complicated way of obtaining the very labile polyacyloins as well as their subsequent condensation with urea considerable difficulties.

Reacting monomeric acyloins, polyamines and polyisocyanates succeeds it to avoid these disadvantages and to produce new polyimidazolin-2-ones, their Monomer units are linked via the nitrogen atoms. These polymers draw characterized by high heat resistance, thermal shock resistance, mechanical strength and resistance to solvents in addition to a high softening point.

The present invention relates to polyimidazolin-2-ones and polythioimidazolin-2-ones of the following formulas in which n = 15-10,000, preferably 20-500, denotes, R1 and R2> identical or different, a hydrogen, aliphatic radical with 1 U 6 carbon atoms, preferably 1-4 carbon atoms, a cycloaliphatic radical with 5-12 carbon atoms, preferably 6 carbon atoms, an aryl radical with 5-12 carbon atoms, which is optionally substituted with an alkyl radical with 1-4 carbon atoms, or with a halogen, or with an alkylaryl or arylalkyl radical 7-10 carbon atoms, R3 and R4 denote one, identical or different, aliphatic radical with 2-10 carbon atoms, preferably 2-6 carbon atoms, cycloaliphatic radical with 5-12 carbon atoms, preferably 6 carbon atoms , Aryl radical with 5-12 carbon atoms, which is optionally substituted with an alkyl radical with 1-4 carbon atoms, a halogen, -CN, alkoxy or -NO2, alkylaryl radical with r -10 carbon atoms or a radical of the general formula R5 - Y - R6 means in-the and R5 and R6 denote one, identical or different, aliphatic radical with 2-6 carbon atoms, aryl radical with 5-12 carbon atoms or cycloaliphatic radical with 5-12 carbon atoms.

The new polyimidazolin-2-ones are obtained by reacting acyloins with polyamines at temperatures between 60 ° C and 500 ° C, preferably at 800 - 35o0C with and without solvent.

The resulting C-amino ketones are in a 2nd stage with Isocyanates or isothiocyanates converted to polyimidazolin-2-ones.

Compounds of the general formula are suitable as acyloins for the process according to the invention wherein R1 and R2 have the meaning given above.

R1 and R2 are preferred, in addition to hydrogen, residues of methane, propane, Cyclohexane, benzene, toluene, xylene and naphthalene, single or multiple with Alkyl, aryl or halogen groups can be substituted.

Suitable acyloins are: Preferably aromatic acyloins such as. B. Benzoin is used.

As polyamines with at least 2 primary amino groups are suitable for the inventive method compounds of the general formula R4 (-NH2) m, in R4 has the meaning given above and m is an integer from 2 to 4.

R4 is preferably derived from ethane, propane, butane, hexane, diethyl ether, Dipropyl sulfide, cyclopentane, cyclohexane, benzene, toluene, xylene, naphthalene, diphenyl, Diphenylmethane, diphenylsulfone, diphenyldimethylmethane, benzophenone, 2,5-diphenyloxadiazole and 2,5-diphenyltriazole. They can be substituted one or more times, for example by alkyl, aryl, alkoxy, cyano, halogen and nitro groups.

Suitable amines are: Preferably aromatic diamines such as. B. p-phenylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether are used.

Suitable as polyiso (thio) cyanates with at least 2 iso (thio) cyanate groups those of the general formula R3 (-NCO) or R (-NCS) m in b are those given above Has meaning and m is an integer from 2 to 4.

Suitable isocyanates are: Preferably aromatic diisocyanates such as. B.

2,4-tolylene diisocyanate, 4,4'-diisocyanatodiphenylmethane and 4, 4? Diisocyanatodiphenylether used.

Instead of isocyanates, isothiocyanates and so-called blocked isocyanates are used, which isocyanates under the reaction conditions split off, such as, for example, the addition products with phenols or CH-acids Links.

The process according to the invention is illustrated by the following reaction scheme: Equation 1 (Formula III) Equation 2 (analogous to formula I) The O (-aminoketones of the formula III can be prepared, for example, by heating the acyloins with polyamines, optionally in a solvent such as glycol monomethyl ether, cresol or cresol / xylene mixtures sometimes already during the reaction and can easily be isolated in high purity.

For the method according to the invention, however, it is not necessary that Isolate intermediate product. You can get in shape right in the same reaction vessel the reaction solution are reacted further. That which arises in the condensation steps Water is either directly or optionally with the addition of suitable inert organic solvents such as preferably chlorobenzene, toluene and xylenes discharged respectively.

azeotropically distilled off, optionally in vacuo. This procedure simplifies the technical production of the polyimidazolin-2-ones considerably.

The inventive method can be carried out in solvents that do not react with the components under the reaction conditions or at most enter into intermediate, reactive addition compounds. For the procedure suitable solvents or dispersants are polar and non-polar solvents like t. B. aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, Phenols, amides, esters, ketones and sulfoxides. As representative be named: phenol, cresols, xylenes, 9-dichlorobenzene, glycol monomethyl ether acetate, Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzophenone, diphenyl carbonate, cyclohexanone as well as their mixtures.

Cresol and N-methylpyrrolidone and mixtures thereof are preferred used.

To carry out the method according to the invention, first the acyloins and polyamines with or without solvents at temperatures between 60 and 5000 ° C., preferably at 80 to 350 ° C., until the calculated Amount of water, optionally removed by azeotropic distillation. Afterward the resulting poly-X-aminoketones are either directly or after intermediates Isolation with the, optionally masked, polyisocyanates or polyisothiocyanates a few minutes to several hours at temperatures from -20 to 5000C, preferably implemented at lo to 350 ° C. The progress or completion of the polymerization can be based on the increasing viscosity of the condensate and the amount of water discharged will. In general, the solvent used when adding isocyanate is also used removed from the water formed in the cyclization step by azeotropic distillation. Occasionally, conversions in the presence of an inert protective gas such as Nitrogen, products with better properties such as B. little colored products, be achieved. The condensation steps can optionally also be carried out in a vacuum, optionally also carried out in the presence of a condensing agent such as diphenyl carbonate will.

Sometimes it is advantageous to use the one that starts after the isocyanate addition Polymerization to be carried out in stages. In the first stage at temperatures from lo to 80 oC the conversion takes place to a low molecular weight product with functional Groups that operate at higher temperatures, possibly with chain extension or crosslinking into the high molecular weight polyimidazoline -2-on is convicted.

According to the invention, the reactions can be accelerated by catalysts will. Possible catalysts are, for example: Tertiary amines such as triethylamine, Tributylamine, N-methyl-morpholine, N-thyl-morpholine, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethyl-piperazine, N, N-dimethylbenzylamine, Bis (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-1,3-butanediamine> N, N-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole.

In addition, hydrogen atoms which are active towards isocyanate groups tertiary amines, e.g. B. triethanolamine, trisopropanolamine, N-methyl-diethanolamine, N-thyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with Alkylene oxides such as propylene oxide and / or ethylene oxide and nitrogenous bases such as Tetraalkylamoniumhydroxide and Hexahydrotriazine or organic or inorganic Metal compounds, in particular iron, lead and / or tin compounds. As organic Tin compounds are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, Tin (lI) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin salts of carboxylic acids, such as. B. dibutyltin dichloride, acetate, laurate, maleate or Dioctyltin diacetate into consideration, also iron salts such as iron acetylacetonate or Ferric chloride, lead oxide, lead carbonate or lead carboxylates.

Further catalysts to be used according to the invention are in the plastics manual, Volume VII, edited by Vieweg and Höchtlen, Carl-Hauser-Verlag, Munich, 1966, Pages 96-102 as well as in High Polymer, Vol.XVI, Part I, Polyurethanes-Chemistry, published by Saunders and Frisch, Interscience Publishers, New York, 1962, Pages 129-217. The catalysts are usually in a lot between 0.001 and 10 percent by weight, based on the solids content of the polymerization batch, used.

The compounds obtained according to the invention can Se according to the reaction condition high molecular weight or low molecular weight.

In general, it is advantageous to use equimolar amounts of the reaction components used. However, the method according to the invention is also applicable in the case of significant deviations feasible from the stoichiometric ratios. So can the reaction components can be used in equimolar amounts in the 1st stage, and in the 2nd stage the t-aminoketones (III) and polyisocyanates and their molar ratios are chosen in this way that high molecular weight or low molecular weight products arise.

If you use z. B. for 1 mole of the i-aminoketone an amount of 2 / m to 4 / m mole of polyiso (thio) cyanate with mNCO groups per molecule, then for m> 1, preferably m = 2, products of the formula are obtained (Formula IV) with n = 1 to about 2'oo and analogously with blocked isocyanates or phenolic solvents, products of the formula (Formula V) in which Ar is an aromatic radical.

Since the reaction is usually carried out in solvents, the products arise as solutions. These solutions can be used directly as a coating agent can be used. They are made from them by heating to around 180 - 5000C, which are temperature-resistant Coatings that are extremely resistant chemically, thermally and physically are. It is to be expected that the iso (thio) still present in the products cyanate groups through chain extension or crosslinking to form high molecular weight Materials lead. Cross-linked substances can, however, also have more than divalent properties Isocyanates or the polyfunctional t-amino ketones already listed above are obtained the proportion of crosslinking component fluctuating within very wide limits can. For example, 1 mole of N, N ', N "-tris-desyl-4,4', 4" -triaminodiphenylmethane is produced and 3 moles of 4,47-diisocyanatodiphenylmethane with one of 3 imidazolin-2-one rings 3, optionally blocked, NCO groups existing oligomers. The "networking Component "can therefore be advantageous in stoichiometric approaches according to equation 2 from a more than difunctional iso (thio) cyanate and / or from a more than difunctional one OC-Aminoketondcriva exist, whereby the proportion of these components to each existing Isocyanate or 0.1 to 50 mol percent of o (-aminoketone groups present, preferably 0.2 to lo mole percent.

The polyimidazolin-2-ones obtainable by the process according to the invention have high thermal stability and thermal shock resistance and are suitable for the production of heat-resistant plastics in the form of threads, foils, moldings and Lacquers.

Their properties can be varied by varying the stoichiometric Conditions, the degree of condensation and the addition of pigments, as well as low- and high molecular weight components can be adapted to the most varied of purposes.

The finished polymer is usually extracted from its solution with water, with lower alcohols such as methanol, ethanol or isopropanol, aromatics such as benzene, Ketones or esters such as acetone or ethyl acetate, preferably precipitated with methanol and, optionally with the addition of dilute alkalis, washed.

The isolated polymers can then, depending on the intended use, for Production of 1 to 99 percent by weight, preferably from 10 to 60 percent by weight Solutions, - such as in dialkylamides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or phenolic solvents such as phenol and cresol as well as their mixtures are dissolved.

In the production of wire enamels or stove enamels, you can the polyimidazolin-2-ones prepared according to the present invention, if appropriate can also be mixed with other polymers such as polyphenylene.

The service life of the polyimidazolin-2-one solutions is practically unlimited. They can generally be processed by baking at temperatures between 80 and 550 ° C can be carried out.

The following examples illustrate the invention. In the trials the technical isomer mixture is used as cresol. The viscosities were measured in a Haake falling ball viscometer from Gebrüder Haake, Berlin.

Example 1 a) 424 g (2 moles) of benzoin and 108 g (1 mole) of p-phenylenediamine are stirred in 1000 ml of technical cresol at 160 ° C. for 6 hours. After discharging the solid is precipitated from approx. 56 g of water with methanol and from dimethylformamide recrystallized.

Yield: 450 g (90% of theory) N, N'-didesyl-p-phenylenediamine, M.p .: 250-252 ° C.

The remaining amino ketones can be prepared analogously to Example 1, for example N, N'-didesyl-4,4'-diaminodiphenylmethane with a melting point of 180-1830C (from Dioxane / alcohol) or N, N'-didesyl-4,4'-diaminodiphenyl ether of melting point: 16o -1610C (from ethyl acetate / alcohol) b) 248.3 g (0.5 mol) of N, N'-didesyl-p-phenylenediamine dissolved with heating in 700 ml of technical cresol, at 70 ° C with the solution of 125.0 g (0.5 mol) of 4,4'-diisocyanatodiphenylmethane in 200 ml of toluene are added and Stirred at 100 ° C. for 3 hours. The reaction temperature is then increased within from about 2 hours to 150 0C and distilled azeotropically with the toluene the calculated Amount of water.

The mixture is then stirred at 180 ° C. for a further 10 hours.

About 1080 g of an about 33% solution of the condensate are obtained a viscosity of 9380 cP 2o0C> which is applied directly to metal sheets or glass plates in 20 minutes at 2000C and a further 10 minutes at 220 ° C to clear, elastic, good adhering paint films can be baked. In the IR spectrum of the film are at 1690 cm for the carbonyl group and 1375 cm for the imidazolin-2-one ring characteristic bands.

Example 2 293.4 g (0.5 mol) of the N, N'-didesyl- 4,4-diaminodiphenylmethane are dissolved in 820 ml of technical cresol in the heat, 0.8 g of endoethylene piperazine added and at 50 ° C with the solution of 87.1 g (0.5 mol) of toluene-2,4-diisocyanate added in 150 ml of xylene and stirred for 3 hours at 100 ° C. Then you increase in the course from about 1.5 hours the temperature to 160 ° C, contributes the appropriate amounts Xylene and water and finally stirred for another 10 hours at 190 ° C. the The viscosity of the approx. 30 solution is 14470 cP 2000. The polySmidazolin-2-one ring structure is confirmed by the typical IR absorption at 1690 cm -1 and at 1375 cm.

When the viscous condensate is burned in at 200 and 2200C, a light brown, clear, tough paint film preserved.

Example 3 293.4 g (0.5 mol) of the N, N'-didesyl-4,4'-diaminodiphenylmethane prepared according to 1 a) are dissolved in the heat in 950 ml of technical cresol, with 0.5 g of endoethylene piperazine and starting at 50 ° C. with the solution of 125.9 g (0.5 mol) of 4,4'-diisocyanatodiphenylmethane added in 150 ml of toluene and stirred at 100 ° C. for 2.5 hours. Then increases if you bring the temperature to 15o0C within about 1 hour, the expected amounts are applied in toluene and water and stir for 10 hours at 18o0C.

The resulting polyimidazolin-2-one solution has after dilution with cresol to a 15 percent solids content a viscosity of 320.0 cP 20 ° C and turns into light brown, clear, elastic paints at 200 and 220 ° C burn in, whose imidazolin-2-one ring structure by the typical IR-Ab-1 -1 sorption is confirmed at 1690 cm 1 and at 1375 cm 1.

A polyimidazolin-2-one solution of the same viscosity is obtained if, for example, 50 g of the reaction solution obtained according to Example 4 with stirred looo ml of methanol and the quantitatively precipitated solid mixed again with cresol to form a 15 percent by weight solution.

Example 4 294.3 g (0.5 mol) of the N, Nt-didesyl-4,4'-diaminodiphenyl ether prepared according to 1 a) are dissolved in 800 ml of technical grade cresol with heating, with 0.8 g of endoethylene piperazine and starting at 40 ° C with the solution of 126.1 g (0.5 mol) of 4,4'-diisocyanate-6diphenyl ether added in 150 ml of toluene and stirred at 90 ° C. for 3 hours. Then you increase the Temperature within about 1.5 hours to 15o0C, distilled the calculated Quantities of toluene and water and finally stirred for a further lo hours at 18o0C. About 1230 g of an approx. 32 polyimidazolin-2-one solution remain, which is a Has a viscosity of 17520cP at 20 ° C. The imidazolin-2-one structure is made possible by the IR bands detected at 1690 cm -1 and at 1375 cm -1.

The resulting polyimidazolin-2-one solution is then mixed with the solution of 200 g of a polyester made from terephthalic acid and ethylene glycol in 350 ml of technical Cresol mixed and at 200 and 220 ° C to a light brown, clear, scratch-resistant Burned in film of excellent flexibility.

Example 5 212.2 g (1 mole) benzoin and 99.1 g (0.5 mole) 4,4'-diaminodiphenylmethane are stirred in 600 ml of technical cresol for 7 hours at 170 ° C, after distillation diluted the calculated amount of water with another 275 ml of technical cresol, then with 0.7 g of endoethylene piperazine and starting at 50 ° C with the solution of 125.0 g (0.5 mol) of 4,4'-diisocyanatodiphenylmethane in 250 ml of toluene are added. After 3 hours Stirring at 90 ° C, the temperature is increased to 150 ° C in the course of 1.5 hours, distills off the appropriate amounts of toluene and water and completes the condensation by lo hour Stir at 18o0C. The viscosity of the approx. 31% Solution is 15230 cP 2o0C.

The lacquer solution obtained in this way gives on stoving at 200 and 220 ° C a smooth, solvent-resistant film and shows in the IR spectrum at 1690 cm 1 for the carbonyl group and at 1375 cm 1 for the imidazolin-2-one ring characteristic bands.

The cresolic solution is poured into about 5000 parts by weight Methanol precipitated. After filtering off with suction and drying, 312 g of a polyimidazolin-2-one are obtained with 6.7% N.

Example 6 212.2 g (1 mol) of benzoin are mixed with 100.1 g (0.5 mol) of 4,4'-diaminodiphenyl ether in a mixture of 450 ml of technical grade cresol and 150 ml of xylene at 170 ° C. for 7 hours touched. After distilling the expected amounts of xylene and water, the Reaction mixture diluted with 350 ml of technical cresol, 0.5 g of endoethylene piperazine added and at 60 ° C starting with the solution of 125.0 g (0.5 mol) of 4,4t-diisocyanatodiphenylmethane added in 180 ml of toluene. The mixture is then stirred for 3 hours at 90 ° C., then increased within an hour the reaction temperature to l5o0C, carries the appropriate Quantities of toluene and water and the mixture is stirred at 180 ° C. for a further lo hours.

The clear, viscous, approx. 33 ige polyimidazolin-2-one solution with a Viscosity of 16100 cP at 20 ° C. is then 200 after adding 0.8 g of butyl titanate and 220 ° C to a light brown, heat-resistant film of great surface hardness burned in.

Example 7 38o g of m-cresol are obtained at 120 ° C according to the exothermic Reaction within about 1 hour with 50.0 g of 4,4t-diisocyanato -diphenylmethane and then added 117.3 g of N, N'-didesyl-4,4'-diaminodiphenylmethane. Man heats the mixture directly to approx. 1850C while passing dry nitrogen through it, carries out the expected amount of water and lasts about 12 hours at 1850C.

This results in approx. 540 g of an approx. 30% cresolic polyimidazolinone solution, the viscosity of which is 21315 cP at 20 ° C and the typical IR absorption at 1690 and 1375 cm-1.

The cresolic solution is made by stirring with approx. Gooo g of methanol pleases. After filtering off with suction and drying, 97 g of a polyimidazolin-2-one are obtained with a nitrogen content of 6.8%.

Example 8 Following the method described in Example 8, 380 g of m-cresol with 50.4 g of 4,4'-diisocyanato-diphenyl ether and then with 117.7 g of N, N'-didesyl-4,4'-diaminodiphenyl ether first at 12o0C, then implemented in a weak vacuum for 14 hours at 175-18o0C.

After the expected amount of water has been discharged, approx. 51Fo g remains of about 30 show polyimidazolin-2-one solution with a viscosity of 24840 cP 2o0C. Their precipitation in methanol gives 76 g of a polyimidazolin-2-one with a Nitrogen content of 6.9%. The imidazolinone structure is determined by the IR absorption Confirmed at 169o and 1375 cm.

Examples 9-12 According to the method described in Example 7 are 380 g (example 9 and lo) or 385 g (example 11) or 39o g (example 12) of m-cresol with 50.0 g (9), 51.0 g (lo), 53.0 g (11) or 55.0 g (12) 4,4'-diisocyanatodiphenylmethane and then mixed with 117.7 g of N, N'-didesyl-4,4'-diaminodiphenyl ether at 120 ° C, direct heated to 185 ° C. with distillation of the water and held there for about 20 hours.

The resulting solution shows in the IR spectrum at 1690 and 1375 cm the typical imidazolinone bands.

In particular, a total of 540 g of solution remain in Example 9 with a Viscosity of 23530 cP 20 ° C, Beispelo a total of 541 g solution with a viscosity of 27192 cP 2o0C, Example 11 a total of 548 g of solution with a viscosity of 35285 cP 2o0C, example 12 a total of 555 g of solution with a viscosity of 14570 cP 2o0C.

Example 13 220 g of m-cresol are successively mixed with 37.5 g of 4,4'-diisocyanatodiphenylmethane and 58.67 g of N, N'-didesyl-4,4'-diaminodiphenylmethane mixed at 120 ° C and then heated under a weak vacuum to 180 ° C, the calculated amount of water is distilled off and held at 180 ° C for 12 hours; The result is 312 g of one in relation to the free one Isocyanates, approx. 30% cresolic oligoimidazolin-2-one solution, its imidazolinone ring structure is proven by the IR absorption at 169o and 1575 cm l. The viscosity is 18460 cP 20 ° C.

The cleavage titration shows a content of 1.7% of what is still available NC0 groups.

Example 14-16 385 g of m-cresol are made with those given below Catalysts mixed, then at 120 ° C initially with 51.0 g of 4,41-diisocyanatodiphenylmethane and finally treated with 117.3 g of N, N'-didesyl-4,4'-diaminodiphenylmethane, under Passing through dried nitrogen heated to 185 0C and the required Amount of water discharged.

After about 12 hours at 185 ° C., the expected Amount of the cresolic solution of a polyimidazolin-2-one, with typical IR absorption at 1690 and 1375 cm1 and the Uiskosities listed below.

Example 14 0.016 g of triethylenediamine Viscosity: 28310 cP 20 ° C. Example 15 0.075 g iron acetylacetonate Viscosity: 30277 cP 200C Example 16 0.018 g PbO Viscosity: 27825 cP 200C Example 17 380 g of m-cresol are at 12000 within of about 1 hour depending on the exothermic reaction with 51.0 g of 4,4'-diisocyanatodiphenylmethane offset. The mixture is heated to 175-1800 and carries 177.7 g of N, N'-didesyl-4,4'-diaminodiphenyl ether and the calculated amount of water is distilled off under a gentle vacuum. After approx. 12 hours at 180 - 18500 results in approx. 541 g of approx. 30 show cresolic PolySmidazolinone solution with a viscosity of 34650 c: 20 ° C and the typical Imidazolinone iR absorption at 1690 and 1375 cm 1 The nitrogen content of a with Methanol precipitated sample is 6.8%.

Example 18 The solution of 0.089 g of dibutyltin dilaurate in 390 g of m-cresol is at 185 ° C according to the exothermic reaction directly with the intimately triturated Mixture of 51.4 g of 4,4t-diisocyanato-diphenyl ether and 117.7 g of N, N'-didesyl, diaminodiphenyl ether added, the calculated amount of water discharged and passing dry Nitrogen held at 185-19000 for about 15 hours.

About 552 g of an approximately 30% cresolic polyimidazolinone solution are obtained with the characteristic IR absorption at 169o and 1375 cm 1 and a viscosity of 27400 cP 20 ° C.

Claims (9)

Patent claims: 1. Poly-4-imidazolin-2-ones or -4-thioimidazolin-2-ones of the following formula in which na 15-10,000, preferably 20-500, denotes R1 and R2, identical or different, a hydrogen, aliphatic radical with 1-6 carbon atoms, preferably 1-4 carbon atoms, a cycloaliphatic radical with 5-12 C atoms, preferably 6 0 atoms, an aryl radical with 5-12 C atoms, which is optionally substituted with an alkyl radical with 1-4 C atoms, or with a halogen, or an alkylaryl or arylalkyl radical with 7-10 C -Atoms mean, R3 and R4 one, identical or different, aliphatic radical with 2-10 carbon atoms, preferably 2-6 0 atoms, cycloaliphatic radical with 5-12 carbon atoms, preferably 6 carbon atoms, aryl radical with 5 - 12 carbon atoms, which is optionally substituted with an alkyl radical with 1-4 0 atoms, a halogen, -CN, @ioxy or -NO2. Alkylaryl radical with 7 - lo atoms or an est of the general formula R5 - Y - R6, in which -Y- for -S-, -0-, -SO2- -CO- H3C-C-CH3, -O- ( CH2) -O- (2-4) or and R5 and R6 denote one, identical or different, aliphatic radical with 2-6 0 atoms, aryl radical with 5-12 carbon atoms or cycloaliphatic radical with 5-12 carbon atoms. 2. Process for the preparation of poly-4-imidazolin-2-ones or poly-4-thioimidazolin-2-ones in a 2-stage condensation, characterized in that moncmere in the 1st stage Acyloins and polyamines, optionally dissolved in a solvent, at temperatures between 600 and 500 ° C are converted to polymeric α-aminoketones and in the 2nd stage at temperatures between 20 to 5000C with these α-amino ketones Polyisocyanates or polyisothiocyanates, if appropriate in a solvent dissolved, optionally in the presence of a condensing agent such as diphenyl cartonate, optionally in vacuo, to poly-4-imidazolin-2-ones b:; w poly-4-thioimidazolin-2-ones react. 3. The method according to claim 2, characterized in that 1 mol of a difunctional t (amino ketone with a polyiso (thio) cyanate containing m NCO groups in an amount of 2 / m to 4 / m mol. 4. The method according to claim 2, characterized in that the Reaction carried out in a solvent containing active hydrogen atoms. 5. The method according to claim 2, characterized in that the Implementation in a phenolic solvent. 6. The method according to claim 2, characterized in that the Implementation in the presence of an organic or inorganic metal compound. 7. The method according to claim 2, characterized in that the Implementation in the presence of metal compounds of Fe, Pb, Zn, Sn. 8. The method according to claim 2, characterized in that the Implementation in the presence of a tert. Amine carries out. 9. Oligo-4-imidazolin-2-ones of the formula IV containing NCO groups where n can be a number from 1 to 200 and R1, R2, R3 and R4 have the meaning given in claim 1. lo. Oligo-4-imidazolin-2-ones of the formula V containing blocked isocyanate groups wherein Ar is an aromatic radical, n is a number from 1 to 200 and R1, R2, R3 and R4 have the meaning given in claim l.