Process for preparing trimers and/or oligomers of diisocyanates

Abstract

A process for preparing trimers and/or oligomers of diisocyanates is disclosed along with a composition of trimers and/or oligomers formed from diisocyanates and monomeric diisocyanates obtainable by reaction of I. 5-94.999% by weight of A) at least one diisocyanate having a boiling point of less than 250 C. (at standard pressure) and/or B) at least one diisocyanate having a boiling point of 250-350 C. (at standard pressure), in the presence of II. 94.999-5% by weight of C) at least one diisocyanate having a boiling point above 350 C. (at standard pressure), III. in the presence of at least one trimerization catalyst in amounts of 0.001% to 5% by weight, and the amounts of I.-III. add up to 100% by weight.

Claims

1. A composition of trimers and/or oligomers formed from diisocyanates and monomeric diisocyanates, the composition comprising the reaction product of I. from 5 to 94.999% by weight of A) an aliphatic and/or cycloaliphatic diisocyanate having a boiling point of less than 250 C. (at standard pressure) and/or B) an aliphatic and/or cycloaliphatic diisocyanate having a boiling point of from 250 to 350 C. (at standard pressure), in the presence of II. from 94.999 to 5% by weight of C) a diisocyanate having a boiling point above 350 C. (at standard pressure) wherein the diisocyanate is selected from the group consisting of dicyclohexylmethylene diisocyanate (H.sub.12MDI) and octadecane diisocyanate, III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight, where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 10% by weight, and based on the diisocyanate A) and/or B) used is not greater than 20% by weight in relative terms.

2. The composition according to claim 1, wherein at least 60% by weight of the components A) and/or B) used has been converted to trimers and/or oligomers, based on the sum total of A) and B) and wherein a step of distillative removal is not required.

3. The composition according to claim 1, wherein the aliphatic and/or cycloaliphatic diisocyanate A) has a boiling point of less than 250 C., selected from the group consisting of butyl diisocyanate and ethyl diisocyanate.

4. The composition according to claim 1, wherein the aliphatic and/or cycloaliphatic diisocyanate B) having a boiling point of from 250 to 350 C., is selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate, mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate ethyl ester and m-xylylene diisocyanate.

5. The composition according to claim 1, wherein the diisocyanate C) is dicyclohexylmethylene diisocyanate (H.sub.12MDI).

6. The composition according to claim 1 comprising the reaction product of I. from 5 to 94.999% by weight of A) the aliphatic and/or cycloaliphatic diisocyanate having a boiling point of less than 250 C. is selected from the group consisting of butyl diisocyanate and ethyl diisocyanate, and/or B) an aliphatic and/or cycloaliphatic diisocyanate having a boiling point of 250-350 C. is selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate, mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), and lysine diisocyanate ethyl ester, in the presence of II. from 94.999 to 5% by weight of C) a diisocyanate having a boiling point above 350 C., selected from the group consisting of dicyclohexylmethylene diisocyanate (H.sub.12MDI) and octadecane diisocyanate, III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight, where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 3% by weight, and based on the aliphatic and/or cycloaliphatic diisocyanate A) and/or B) used is not greater than 6% by weight in relative terms.

7. The composition according to claim 1 comprising the reaction product of I. from 5 to 94.999% by weight of B) isophorone diisocyanate (IPDI) in the presence of II. from 94.999 to 5% by weight of C) dicyclohexylmethylene diisocyanate (H.sub.12MDI), III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight.

8. The composition according to claim 1, wherein the trimerization catalysts III. are selected from the group consisting of tertiary amines, alkali metal salts of carboxylic acids, quaternary ammonium salts, aminosilanes, quaternary hydroxyalkylammonium salts, quaternary phosphonium salts, on their own or in mixtures.

9. The composition according to claim 1, wherein trimerization catalysts III. are selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts are used, on their own or in mixtures.

10. The composition according to claim 1, wherein trimerization catalysts III. are selected from the group consisting of quaternary tetraalkylammonium salts and quaternary phosphonium salts, with halogens, hydroxides, alkoxides or organic or inorganic acid anions as counterion, are used, on their own or in mixtures.

11. The composition according to claim 1, wherein the trimerization catalyst III. is tetraethylammonium hydroxide.

12. A process for producing compositions of trimers and/or oligomers from diisocyanates and monomeric diisocyanates comprising the steps of reacting I. from 5 to 94.999% by weight of A) an aliphatic and/or cycloaliphatic diisocyanate having a boiling point of less than 250 C. and/or B) an aliphatic and/or cycloaliphatic diisocyanate having a boiling point of 250-350 C., in the presence of II. from 94.999 to 5% by weight of C) a having a boiling point above 350 C. wherein the diisocyanate is selected from the group consisting of dicyclohexylmethylene diisocyanate (H.sub.12MDI) and octadecane diisocyanate, III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight, where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the aliphatic and/or cycloaliphatic diisocyanate A) and/or B) used is not greater than 40% by weight in relative terms.

13. A process according to claim 12, wherein the reaction is effected at temperatures of 0 to 140 C.

14. A paint comprising the reaction product of I. from 5 to 94.999% by weight of A) an aliphatic and/or cycloaliphatic having a boiling point of less than 250 C. and/or B) an aliphatic and/or cycloaliphatic diisocyanate having a boiling point of 250-350 C., in the presence of II. from 94.999 to 5% by weight of C) a having a boiling point above 350 C. wherein the diisocyanate is selected from the group consisting of dicyclohexylmethylene diisocyanate (H.sub.12MDI) and octadecane diisocyanate, III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight, where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the aliphatic and/or cycloaliphatic diisocyanate A) and/or B) used is not greater than 40% by weight in relative terms, in paints, adhesives, sealants and/or plastics.

15. The process according to claim 12, wherein the aliphatic and/or cycloaliphatic A) has a boiling point of less than 250 C., selected from the group consisting of butyl diisocyanate and ethyl diisocyanate.

16. The process according to claim 12, wherein the aliphatic and/or cycloaliphatic diisocyanate B) having a boiling point of from 250-350 C. is selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate, mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate ethyl ester and m-xylylene diisocyanate.

17. The process according to claim 12, wherein the diisocyanate C) is dicyclohexylmethylene diisocyanate (H.sub.12MDI).

18. The process according to claim 12, comprising the steps of reacting I. from 5 to 94.999% by weight of A) the aliphatic and/or cycloaliphatic diisocyanate having a boiling point of less than 250 C. is selected from the group consisting of butyl diisocyanate and ethyl diisocyanate, and/or B) the aliphatic and/or cycloaliphatic diisocyanate having a boiling point of 250-350 C. is selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate, mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate ethyl ester and m-xylylene diisocyanate, in the presence of II. from 94.999 to 5% by weight of C) octadecane diisocyanate, III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight, where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the aliphatic and/or cycloaliphatic diisocyanate A) and/or B) used is not greater than 40% by weight in relative terms.

19. The process according to claim 12, comprising the steps of reacting I. from 5 to 94.999% by weight of B) isophorone diisocyanate (IPDI) in the presence of II. from 94.999 to 5% by weight of C) dicyclohexylmethylene diisocyanate (H.sub.12MDI), III. in the presence of at least one trimerization catalyst in amounts of from 0.001% to 5% by weight, and the amounts of add up to 100% by weight, where the proportion of monomeric B) after the reaction in the mixture, based on the overall mixture of B)+C), in absolute terms is not greater than 20% by weight, and based on the aliphatic and/or cycloaliphatic diisocyanate B) used is not greater than 40% by weight in relative terms.

20. The process according to claim 12, comprising the steps of reacting, wherein the trimerization catalysts III. are selected from the group consisting of tertiary amines, alkali metal salts of carboxylic acids, quaternary ammonium salts, aminosilanes, quaternary hydroxyalkylammonium salts, quaternary phosphonium salts, on their own or in mixtures.

Description

DETAILED DESCRIPTION

(1) It has been found that, surprisingly, diisocyanates having a boiling point above 350 C., for example H12MDI, can be used as solvents in order to trimerize volatile and/or moderately volatile diisocyanates therein, such that it is possible to dispense with the distillative removal of the monomeric volatile and/or moderately volatile diisocyanates.

(2) The invention provides a composition of trimers and/or oligomers formed from diisocyanates and monomeric diisocyanates,

(3) obtainable by reaction of

(4) I. 5-94.999% by weight of A) at least one diisocyanate having a boiling point of less than 250 C.

(5) and/or B) at least one diisocyanate having a boiling point of 250-350 C.,

(6) in the presence of

(7) II. 94.999-5% by weight of C) at least one diisocyanate having a boiling point above 350 C.,

(8) III. in the presence of at least one trimerization catalyst in amounts of 0.001% to 5% by weight,

(9) and the amounts of add up to 100% by weight,

(10) where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the diisocyanate A) and/or B) used is not greater than 40% by weight in relative terms.

(11) This means that at least 60% by weight of the components A) and/or B) used have been converted to trimers and/or oligomers, based on the sum total of A) and B).

(12) The invention provides a process for producing compositions of trimers and/or oligomers from diisocyanates and monomeric diisocyanates,

(13) obtainable by reaction of

(14) I. 5-94.999% by weight of A) at least one diisocyanate having a boiling point of less than 250 C.

(15) and/or B) at least one diisocyanate having a boiling point of 250-350 C.,

(16) in the presence of

(17) II. 94.999-5% by weight of C) at least one diisocyanate having a boiling point above 350 C.,

(18) III. in the presence of at least one trimerization catalyst in amounts of 0.001% to 5% by weight,

(19) and the amounts of I.-II. add up to 100% by weight,

(20) where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the diisocyanate A) and/or B) used is not greater than 40% by weight in relative terms.

(21) This means that at least 60% by weight of the components A) and/or B) used have been converted to trimers and/or oligomers, based on the sum total of A) and B).

(22) The invention also provides for the use

(23) of the composition of trimers and/or oligomers formed from diisocyanates and monomeric diisocyanates,

(24) obtainable by reaction of

(25) I. 5-94.999% by weight of A) at least one diisocyanate having a boiling point of less than 250 C.

(26) and/or B) at least one diisocyanate having a boiling point of 250-350 C.,

(27) in the presence of

(28) II. 94.999-5% by weight of C) at least one diisocyanate having a boiling point above 350 C.,

(29) III. in the presence of at least one trimerization catalyst in amounts of 0.001% to 5% by weight,

(30) and the amounts of add up to 100% by weight,

(31) where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the volatile or moderately volatile diisocyanate A) or B) used is not greater than 40% by weight in relative terms,

(32) in paints, adhesives, sealants and/or plastics.

(33) The trimerization of diisocyanates is known and has already been described frequently. In principle, polyisocyanurates are obtained by catalytic trimerization of suitable diisocyanates. The trimerization according to the invention affords pure trimers and/or oligomeric trimers, or mixed trimers or mixed oligomers.

(34) Suitable diisocyanates A) and B) in the context of this invention are volatile diisocyanates A) and/or moderately volatile diisocyanates B), preferably aliphatic and/or cycloaliphatic diisocyanates.

(35) In principle, diisocyanates suitable for trimerization can be prepared by various methods (Annalen der Chemie 562 (1949), p. 75ff.). A particularly useful method in industry has been found to be the preparation by phosgenation of organic polyamines to give the corresponding polycarbamoyl chlorides and the thermal cleavage thereof to organic polyisocyanates and hydrogen chloride. Alternatively, organic polyisocyanates can also be prepared without use of phosgene, i.e. by phosgene-free methods. According to EP-A-126 299 (U.S. Pat. No. 4,596,678), EP-A-126 300 (U.S. Pat. No. 4,596,679) and EP-A-355 443 (U.S. Pat. No. 5,087,739), for example, (cyclo)aliphatic diisocyanates such as 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI) can be made available by reacting the parent (cyclo)aliphatic diamines with urea and alcohols to give (cyclo)aliphatic biscarbamoyl esters and thermal cleavage thereof to give the corresponding diisocyanates and alcohols.

(36) All the boiling points listed here for definition of volatility (at standard pressure (SP)=1013 mbar) have either been taken from the literature or else have been converted from literature data from the boiling points at lower pressures. For this purpose, the following Sigma-Aldrich conversion program from the Internet was used: http://www.sigmaaldrich.com/chemistry/solvents/learning-center/nomo-assets.html.

(37) If no literature data were known, the boiling point was estimated with the aid of Advanced Chem. Develop. Software V11.02, from 2016.

(38) Volatile diisocyanates A) are, for example, butyl diisocyanate, b.p.: 228 C. (SP), converted from 112-113 C. at 19 Torr (J. Polym. Sci., 1964, V 2(8; Pt. A), P 3387-404) and ethyl diisocyanate, b.p.: 189 C. (SP), converted from 81 C. at 20 Torr (Journal of Polymer Science 1964, V 2(8; Pt. A), P 3387-404).

(39) Moderately volatile diisocyanates B) are, for example, isophorone diisocyanate (IPDI), b.p.: 295 C. (SP), converted from 217 C. at 100 Torr (National Institute for Occupational Safety and Health), hexamethylene diisocyanate (HDI), b.p.: 255 C. (SP, Prog. in org. Coatings, 2010, V 69(4), P 426-341), norbonane diisocyanate, b.p.: 31315 C. (SP, calculated with Advanced Chem. Develop. Software V11.02), mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), b.p.: 284 C. (SP, calculated with Advanced Chem. Develop. Software V11.02), lysine diisocyanate ethyl ester, b.p.: 30537 C. (SP, calculated with Advanced Chem. Develop. Software V11.02) and m-xylylene diisocyanate, b.p.: 297 C. (SP), converted from 159-162 C. at 12 Torr (Annalen der Chemie, 1949, V 562, P 75-136).

(40) A preferred moderately volatile diisocyanate B) is IPDI.

(41) Sparingly volatile diisocyanates C) are, for example, dicyclohexylmethylene diisocyanate (H.sub.12MDI), b.p.: 410 C. (SP), converted from 156-158 C. at 0.1 Torr from Annalen der Chemie, 1949, 562, P 75-136 and octadecane diisocyanate, b.p.: 43518 C. (SP, calculated with Advanced Chem. Develop. Software V11.02).

(42) A preferred sparingly volatile diisocyanate C) is H.sub.12MDI.

(43) The invention preferably provides a composition of trimers and/or oligomers formed from diisocyanates and monomeric diisocyanates,

(44) obtainable by reaction of

(45) I. 5-94.999% by weight of A) at least one diisocyanate having a boiling point of less than 250 C., selected from butyl diisocyanate and ethyl diisocyanate,

(46) and/or B) at least one diisocyanate having a boiling point of 250-350 C. selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate, mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate ethyl ester and/or m-xylylene diisocyanate,

(47) in the presence of

(48) II. 94.999-5% by weight of C) at least one diisocyanate having a boiling point above 350 C., selected from dicyclohexylmethylene diisocyanate (H12MDI) and/or octadecane diisocyanate,

(49) III. in the presence of at least one trimerization catalyst in amounts of 0.001% to 5% by weight,

(50) and the amounts of I.-III. add up to 100% by weight,

(51) where the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the diisocyanate A) and/or B) used is not greater than 40% by weight in relative terms.

(52) The invention most preferably provides a composition of trimers and/or oligomers formed from diisocyanates and monomeric diisocyanates,

(53) obtainable by reaction of

(54) I. 5-94.999% by weight of

(55) B) isophorone diisocyanate (IPDI)

(56) in the presence of

(57) II. 94.999-5% by weight of

(58) C) dicyclohexylmethylene diisocyanate (H12MDI),

(59) III. in the presence of at least one trimerization catalyst in amounts of 0.001% to 5% by weight,

(60) and the amounts of I.-III. add up to 100% by weight,

(61) where the proportion of monomeric B) after the reaction in the mixture, based on the overall mixture of B)+C), in absolute terms is not greater than 20% by weight, and based on the diisocyanate B) used is not greater than 40% by weight in relative terms.

(62) Suitable trimerization catalysts are, for example, tertiary amines (U.S. Pat. No. 3,996,223), alkali metal salts of carboxylic acids (CA 2113890; EP 56159), quaternary ammonium salts (EP 798299; EP 524501; U.S. Pat. Nos. 4,186,255; 5,258,482; 4,503,226; U.S. Pat. No. 5,221,743), aminosilanes (EP 197864; U.S. Pat. No. 4,697,014) and quaternary hydroxyalkylammonium salts (EP 17998; U.S. Pat. No. 4,324,879) and/or quaternary phosphonium salts. Depending on the catalyst, the use of various co-catalysts is also possible, for example OH-functionalized compounds or Mannich bases formed from secondary amines and aldehydes or ketones.

(63) For the reaction, the diisocyanates are left to react in the presence of the catalyst, optionally with use of solvents and/or auxiliaries, until the desired conversion has been attained. Thereafter, the reaction can be stopped by deactivating the catalyst. This is done by adding a catalyst inhibitor. With regard to the trimerization of diisocyanates on the industrial scale, particular preference is given to the use of quaternary hydroxyalkylammonium carboxylates as catalysts. This type of catalyst is thermally labile and allows controlled thermal deactivation, and so it is unnecessary to stop the trimerization on attainment of the desired conversion by metered addition of potentially quality-reducing inhibitors.

(64) Catalysts used are preferably quaternary ammonium salts on their own or in mixtures, more preferably tetraalkylammonium salts and/or quaternary phosphonium salts, with halogens, hydroxides, alkoxides or organic or inorganic acid anions as counterion.

(65) Examples of these are:

(66) tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and tetrabutylammonium benzoate, and tetrabutylphosphonium acetate, tetrabutylphosphonium formate and ethyltriphenylphosphonium acetate, tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate, methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide, methyltributylammonium methoxide, methyltriethylammonium methoxide, tetramethylammonium methoxide, tetraethylammonium methoxide, tetrapropylammonium methoxide, tetrabutylammonium methoxide, tetrapentylammonium methoxide, tetrahexylammonium methoxide, tetraoctylammonium methoxide, tetradecylammonium methoxide, tetradecyltrihexylammonium methoxide, tetraoctadecylammonium methoxide, benzyltrimethylammonium methoxide, benzyltriethylammonium methoxide, trimethylphenylammonium methoxide, triethylmethylammonium methoxide, trimethylvinylammonium methoxide, methyltributylammonium ethoxide, methyltriethylammonium ethoxide, tetramethylammonium ethoxide, tetraethylammonium ethoxide, tetrapropylammonium ethoxide, tetrabutylammonium ethoxide, tetrapentylammonium ethoxide, tetrahexylammonium ethoxide, tetraoctylammonium methoxide, tetradecylammonium ethoxide, tetradecyltrihexylammonium ethoxide, tetraoctadecylammonium ethoxide, benzyltrimethylammonium ethoxide, benzyltriethylammonium ethoxide, trimethylphenylammonium ethoxide, triethylmethylammonium ethoxide, trimethylvinylammonium ethoxide, methyltributylammonium benzylate, methyltriethylammonium benzylate, tetramethylammonium benzylate, tetraethylammonium benzylate, tetrapropylammonium benzylate, tetrabutylammonium benzylate, tetrapentylammonium benzylate, tetrahexylammonium benzylate, tetraoctylammonium benzylate, tetradecylammonium benzylate, tetradecyltrihexylammonium benzylate, tetraoctadecylammonium benzylate, benzyltrimethylammonium benzylate, benzyltriethylammonium benzylate, trimethylphenylammonium benzylate, triethylmethylammonium benzylate, trimethylvinylammonium benzylate, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammonium chloride, phenyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropylammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide and phenyltrimethylammonium iodide, methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. These catalysts may be added alone or in mixtures. Preference is given to using tetraethylammonium hydroxide.

(67) According to the invention, the trimerization is conducted either batchwise or continuously. The batchwise method is preferred. The batchwise method in a stirred reactor is generally conducted at ambient pressure (standard pressure, 1013 mbar), but other pressures are also possible. This involves initially charging a mixture of 94.999-5% by weight of C) and 5-94.999% by weight of a further volatile diisocyanate A) and/or moderately volatile diisocyanate B). First the mixture of the diisocyanates is preheated to a temperature of 0-140 C., preferably of 55-90 C., more preferably of 65-75 C., then the catalyst is metered in in amounts of 0.001% to 5% by weight; the trimerization is exothermic. The catalyst is first metered in in such an amount that a distinct rise in the temperature of the reaction mixture by 5-15 C. is apparent. Since the catalyst is deactivated in the course of the reaction, the temperature of the reaction mixture drops again over the course of the reaction and a new metered addition of catalyst can be effected. This operation is repeated until the desired conversion has been attained. The sequence of catalyst deactivation and re-initiation of the trimerization by replenishment of catalyst in portions allows optimal process control at any time, both in relation to the conversion and with regard to the temperature profile of the reaction.

(68) The catalyst can be used in pure form. However, for more exact metered addition and optimal mixing of the catalyst, it is advantageous to dissolve the catalyst in a suitable solvent. Suitable solvents in principle are those in which the catalyst has good solubility, for example water, low molecular weight alcohols such as methanol or ethylene glycol, or lower molecular weight organic acids, for example acetic acid or hexanoic acid.

(69) The continuous trimerization can be conducted in a stirred tank cascade. Also conceivable is a combination of stirred tank cascade and tubular reactor.

(70) To restrict the necessary amount of catalyst based on the conversion desired, the temperature profile of the process according to the invention should be set up such that the reaction solution as far as possible does not exceed a temperature of 95 C.

(71) After the trimerization reaction, it is optionally possible to add a catalyst poison, but this is usually unnecessary.

(72) The resultant composition according to the invention comprises, as well as the residual monomers, also pure and mixed trimerizates and oligomerizates of the diisocyanates A) and/or B) and C) used. This mixture can be used as it is or in blends as NCO component in paint, adhesive, sealant or plastic formulations.

(73) The trimerization is continued to such an extent that the proportion of monomeric A) and/or monomeric B) after the reaction in the mixture, based on the overall mixture of A)+B)+C), in absolute terms is not greater than 20% by weight, and based on the volatile or moderately volatile diisocyanate A) or B) used is not greater than 40% by weight in relative terms.

(74) Preference is given to absolute values of <10% by weight and, in relative terms, <20% by weight. Particular preference is given to values of <3% by weight in absolute terms and <6% by weight in relative terms.

EXAMPLES

(75) General Procedure

(76) A mixture of 70% by weight of VESTANAT H.sub.12MDI, C) dicyclohexylmethylene diisocyanate,

(77) (b.p.: 410 C. Evonik Industries AG) and 30% by weight of VESTANAT IPDI, B) isophorone diisocyanate (IPDI), (b.p.: 295 C., Evonik Industries AG) in a stirred three-neck flask is heated up to a particular starting temperature and a catalyst (tetraethylammonium hydroxide, TEAOH, Aldrich) is added, whereupon an exothermic reaction sets in immediately. After the catalyst has been added, the heat source is removed and the product cools down gradually after a few minutes of the exothermic reaction. After cooling, the amount of p-toluenesulfonic acid (Aldrich) equivalent to the catalyst is added. 91 g of tetraethylammonium hydroxide here correspond to 172 g of p-toluenesulfonic acid.

(78) TABLE-US-00001 NCO Free IPDI Catalyst Starting content Temp. (relative to TEAOH [% temperature [% by maximum output) Free H.sub.12MDI by wt.] [ C.] wt.] [ C.] [% by wt.] [% by wt.] Experiment 1 0.25 80 24.2 131 3.7 (10.2) 49.2 Experiment 2 0.25 100 25.9 137 7.4 (24.7) 54.4 Experiment 3 0.5 80 21.2 142 0.5 (1.7) 37.1 Experiment 4 0.2 80 24.7 128 4.7 (15.7) 51.3 Experiment 5 0.1 80 27.3 120 10.4 (34.7) 62.8

(79) The residual monomer content of IPDI in all experiments is less than 20% by weight (free IPDI, left-hand column, absolute). Based on the IPDI used, a relative residual monomer content of 40% by weight is to be observed (free IPDI, right-hand column in brackets, relative), calculated from:
(Final concentration of IPDI/starting concentration of IPDI)100=relative residual monomer content of IPDI