Method for preparing isocyanate-terminated polyoxazolidinones

Abstract

The present invention relates to a method for producing an isocyanate-terminated polyoxazolidinone, which comprises copolymerizing a polyisocyanate compound (A) having two or more isocyanate groups with a polyepoxide compound (B) having two or more epoxy groups in the presence of a specific catalyst (C), wherein the molar ratio of the isocyanate groups of the polyisocyanate compound (B) to the epoxy groups of the polyepoxide compound (A) is greater than 2:1 and less than 25:1. The present invention also relates to the resulting isocyanate-terminated polyoxazolidinone.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an isocyanate-terminated polyoxazolidinone, which comprises copolymerizing a polyisocyanate compound (A) having two or more isocyanate groups with a polyepoxide compound (B) having two or more epoxy groups in the presence of a specific catalyst (C), wherein the molar ratio of the isocyanate groups of the polyisocyanate compound (A) to the epoxy groups of the polyepoxide compound (B) is greater than 2:1 and less than 25:1. The present invention also relates to the resulting isocyanate-terminated polyoxazolidinone. [Background technology]

[0002] Oxazolidinones are structural motifs widely used in pharmaceutical applications, and the cycloaddition of epoxides and isocyanates is considered a convenient one-pot synthetic route to oxazolidinones. In early reports on the synthesis of oxazolidinones, expensive catalysts, reactive polar solvents, long reaction times, and poor chemoselectivity are common (Non-Patent Document 1). These disadvantages have created a need for alternative methods to prepare oxazolidinones, particularly for their application as structural motifs in polymer applications.

[0003] The scientific literature, Non-Patent Document 2, discloses polyoxazolidinones prepared from various bis-epoxides and various diisocyanates in the presence of an alkali metal halide catalyst. A solution of equimolar amounts of the bis-epoxide and diisocyanate was added dropwise to a reactor containing LiCl catalyst dissolved in DMF under reflux conditions within 1 hour, and a subsequent post-reaction of 12 to 23 hours was carried out under reflux conditions to complete the reaction.

[0004] Patent Document 1 teaches a polymer containing oxazolidinone and carbodiimide prepared from polyisocyanate and polyepoxide (these compounds can be diisocyanate or diepoxide), in which the ratio of the number of isocyanate groups to the number of epoxide groups is 1.1:1 to 20:1, preferably 1.2:1 to 10:1, and tertiary aliphatic, alicyclic and aromatic amines such as triethylenediamine (DABCO) are used as catalysts for the formation of oxazolidinone.

[0005] Non-Patent Document 3 discloses the preparation of an isocyanate-terminated polyoxazolidinone in which 4-toluene-2,4-diisocyanate and diglycidyl ether of bisphenol A are reacted in the presence of ytterbium triflate, with the molar ratio of 4-toluene-2,4-diisocyanate to diglycidyl ether of bisphenol A being 2:1.

[0006] In Non-Patent Document 4, the formation of oxazolidinones by the reaction of 4,4-methylenediphenyl diisocyanate (MDI) with o-cresyl glycidyl ether (OGCE) or bisphenol A diglycidyl ether (BADGE) in the presence of various tetra-n-butylammonium halides was investigated, where molar ratios of BADGE to MDI ranging from 1:3 to a maximum of 3:1 were applied. However, when a BADGE to MDI ratio of 3:1 was used, a significant amount of by-product, i.e., isocyanurate, was detected, and epoxy-terminated oxazolidinones were formed. When a BADGE to MDI molar ratio of 1:3 was applied, isocyanate-terminated oxazolidinone formation was not possible in the presence of the applied tetra-n-butylammonium halide catalyst. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 4,129,695 [Non-patent literature]

[0008] [Non-Patent Document 1] ME Dyen and D. Swern, Chem. Rev., 67, 197, 1967 [Non-patent document 2] J. Polym. Sci. 8 (1970) 2759-2773 [Non-patent document 3] Flores et al. (Thermochmica Acta (Elsevier) Vol. 543 (2012) pages 188 to 196) [Non-patent document 4] Pelzer et al. (European Polymer Journal 107 (2018)) Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, the object of the present invention was to identify a simple one-step process for the preparation of isocyanate-terminated polyoxazolidinones having a defined isocyanate equivalent weight, preferably combined with low polydispersity, for further polymerization applications. In this connection, it is necessary to reduce or, advantageously, completely avoid side reactions, such as those due to the formation of isocyanurates or polyurethanes, which lead to an increase in the viscosity of the product. In addition, it is also desirable that the oxazolidinone products have a low color compared to systems described in the prior art, and that such isocyanate-terminated polyoxazolidinone prepolymer systems be meltable for further polymerization applications. [Means for solving the problem]

[0010] Surprisingly, the problem has been solved by a method for preparing an isocyanate-terminated polyoxazolidinone, comprising copolymerizing a polyisocyanate compound (A) having two or more isocyanate groups and a polyepoxide compound (B) having two or more epoxy groups in the presence of a catalyst (C), optionally in a solvent (D), wherein the molar ratio of the isocyanate groups of the polyisocyanate compound (A) to the epoxy groups of the polyepoxide compound (B) is greater than 2:1 and less than 25:1, and the catalyst (C) is Li(I), Rb(I), Cs(I), Ag(I), Au(I), Mg(II), Ca(II), Sr(II), Ba(II), Dy(II), Cu(II), Zn(II), V(II), Mo(II), Mn(II), Fe(II), Co(II), Ni(II), Pd(II), Pt(II), Ge(II), Sn(II), Sc(III), Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Lu(III), Hf(III), Nb(III), Ta(III), Cr(III), Ru(III), Os(III), Rh(III), Ir(III), Al(III), Ga(III), In(III), Tl(III), Ge(III), Ce(IV), Ti(IV), Zr(IV), Hf(IV), Nb(IV), Mo(IV), W(IV), Ir(IV), Pt(IV), Sn(IV), Pb(IV), Nb(V), Ta(V), Bi(V), Mo(VI), W(VI), and Formula (I): [M(R1)(R2)(R3)(R4)]+n Yn- (I) wherein M is phosphorus or antimony, preferably phosphorus; (R1), (R2), (R3), and (R4) are each independently selected from the group consisting of a linear or branched alkyl group containing 1 to 22 carbon atoms optionally substituted with a heteroatom and / or a heteroatom-containing substituent, an alicyclic group containing 3 to 22 carbon atoms optionally substituted with a heteroatom and / or a heteroatom-containing substituent, a C1-C3 alkyl-bridged alicyclic group containing 3 to 22 carbon atoms optionally substituted with a heteroatom and / or a heteroatom-containing substituent, and an aryl group containing 6 to 18 carbon atoms optionally substituted with one or more alkyl groups and / or heteroatom-containing substituents and / or heteroatoms containing 1 to 10 carbon atoms, Y is a halide anion, a carbonate anion, a nitrate anion, a sulfate anion, or a phosphate anion, more preferably a halide anion or a carbonate anion, and n is an integer of 1, 2, or 3; It has been found that the above-mentioned problems can be solved by a method comprising using at least one compound selected from the group consisting of:

[0011] As used herein, the term "polyoxazolidinone" is intended to denote a compound containing at least two oxazolidinone groups in the molecule. The term "isocyanate-terminated" polyoxazolidinone relates to a polyoxazolidinone compound having a molar ratio of isocyanate groups of the polyisocyanate compound (A) to epoxy groups of the polyepoxide compound (B) of greater than 2:1, and no terminal epoxy groups are present in the polyoxazolidinone compound according to the present invention.

[0012] In one embodiment of the method according to the invention, the copolymerization process is carried out at a reaction temperature of from 130° C. to 280° C., preferably from 140° C. to 240° C., more preferably from 155° C. to 210° C. At temperatures below 130° C., the reaction generally proceeds very slowly. At temperatures above 280° C., the amount of undesired by-products increases significantly.

[0013] In one embodiment of the method according to the present invention, the copolymerization process is carried out for a reaction time of 10 minutes to 20 hours, preferably 20 minutes to 10 hours, more preferably 30 minutes to 6 hours.

[0014] As used herein, the term "polyisocyanate compound" is intended to denote a compound having two or more isocyanate groups.

[0015] In one embodiment of the process according to the invention, the polyisocyanate compound (A) is an aliphatic or cycloaliphatic polyisocyanate compound (A-1) and / or an araliphatic or aromatic polyisocyanate compound (A-2), preferably an aliphatic polyisocyanate compound (A-1).

[0016] In one embodiment of the process according to the invention, the polyisocyanate compound (A) is at least one polyisocyanate which is obtainable in various ways, for example by phosgenation in the liquid or gas phase, or by phosgene-free routes, for example by thermal urethane cleavage.

[0017] In one embodiment of the method according to the present invention, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates having aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups in the molecular weight range of 140 g / mol to 600 g / mol, examples of which include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethyl-2,2-dimethyl-1,5-diisocyanatopent ... methylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,12-diisocyanatododecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-Dicyclohexylpropane, 1-isocyanato-1-methyl-4(3)isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbornane or simple fatty acids, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200, in DE-A-1670666, DE-A-1954093, DE-A-2414413, DE-A-2452532, DE-A-2641380, DE-A-3700209, DE-A-3900053 and DE-A-3928503 or in EP-A-0336205, EP-A-0339396 and EP-A-0798299. Any polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure prepared by modification of aromatic and / or cycloaliphatic diisocyanates, such as those of the types mentioned above, or mixtures of at least two such polyisocyanates, as well as 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropanol), 1,3-bis(isocyanatomethyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4- Bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)-5-tert-butylbenzene, 1,3-bis(isocyanatomethyl)-4-chlorobenzene, 1,3-bis(isocyanatomethyl)-4,5-dichlorobenzene, 1,3-bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-Tetrabromobenzene, 1,4-bis(2-isocyanatoethyl)benzene and 1,4-bis(isocyanatomethyl)naphthalene, 1,2-, 1,3- and 1,4-diisocyanatobenzene (phenylene diisocyanate), 2,4- and 2,6-diisocyanatotoluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, isomeric diethylphenylenediisocyanates Isocyanates, diisopropylphenylene diisocyanate, diisododecylphenylene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-Diisocyanatonaphthalene (NDI), diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, diethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, triisocyanatobenzene, 2,4,6-triisocyanatotoluene, trimethylbenzene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, isomeric naphthalene triisocyanates and methylnaphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'-pentaisocyanate, also polynuclear homologues of diisocyanatodiphenylmethane known as "polymer-MDI", and also those described, for example, in DE 870400, DE 953012, DE 1090196, EP 0546399, CN 105218780, CN 1038 81050, Chinese Patent No. 101717571, U.S. Patent No. 3183112, European Patent Application Publication No. 0416338, European Patent Application Publication No. 0751163, European Patent Application Publication No. 1378529, European Patent Application Publication No. 1378530, European Patent Application Publication No. 2174967, Japanese Patent Application Laid-Open No. 63-260915 or Japanese Patent Application Laid-Open No. 56-059828 Polyisocyanates having a urethane and / or isocyanurate structure, obtainable by any of the known methods described above, from monomeric 2,4- and / or 2,6-TDI by reaction with polyols and / or oligomerization, preferably trimerization, or mixtures of at least two such polyisocyanates, as well as polyisocyanate compounds containing both aromatic and aliphatic isocyanate groups, such as the mixed trimers or allophanates of 2,4- and / or 2,6-TDI and HDI described in DE-A-1 670 667, EP-A-0 078 991, EP-A-0 696 606 and EP-A-0 807 623.

[0018] More preferably, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates having aliphatic, alicyclic, araliphatic and / or aromatically bonded isocyanate groups in a molecular weight range of 140 g / mol to 600 g / mol, examples of which include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2, 4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-dicyclohexylpropane, or, for example, J. Prakt. Chem. 336 (1994) 185- 200, modifications of simple aliphatic and / or cycloaliphatic diisocyanates as described in DE-A-1 670 666, DE-A-1 954 093, DE-A-2 414 413, DE-A-2 452 532, DE-A-2 641 380, DE-A-3 700 209, DE-A-3 900 053 and DE-A-3 928 503 or EP-A-0 336 205, EP-A-0 339 396 and EP-A-0 798 299 any polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure, such as those of the type described above, as well as 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 1,3-bis(isocyanatomethyl)-4-methylbenzene, 1,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3-bis(isocyanatomethyl)-5-methylbenzene, 1,3-bis(isocyanatomethyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)- (trimethyl)-5-tert-butylbenzene, 1,4-bis(2-isocyanatoethyl)benzene, 1,4-bis(isocyanatomethyl)naphthalene, 1,2-, 1,3-, and 1,4-diisocyanatobenzene (phenylene diisocyanate), 2,4- and 2,6-diisocyanatotoluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, diisopropylphenylene diisocyanate diisocyanate, diisododecylphenylene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI), diphenyl ether diisocyanate ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, triisocyanatobenzene, 2,4,6-triisocyanatotoluene, trimethylbenzene triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, isomeric naphthalene triisocyanates and methyl naphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-Diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, also polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric MDI", and furthermore, for example, in German Patent Application Publication No. 870400, German Patent Application Publication No. 953012, German Patent Application Publication No. 1090196, European Patent Application Publication No. 0546399, Chinese Patent No. 105218780, Chinese Patent No. 103881050, Chinese Patent No. 101717571, U.S. Patent No. 3183112, European Patent Application Publication No. 0416338, European Patent Application Publication No. 0751163, European Patent Application Publication No. 1378529, European Patent Application Publication No. 1378530, European Patent Application Publication No. 2174967, Japanese Patent Application Laid-Open No. 2004-2008, Polyisocyanates having a urethane and / or isocyanurate structure, which can be obtained by reaction of monomeric 2,4- and / or 2,6-TDI with polyols and / or oligomerization, preferably trimerization, which can be obtained by any known method, as described in German Patent Application Publication No. 63-260915 or Japanese Patent Application Publication No. 56-059828, as well as polyisocyanate compounds having both aromatic and aliphatic isocyanate groups, such as the mixed trimers or allophanates of 2,4- and / or 2,6-TDI and HDI, as described in German Patent Application Publication No. 1670667, European Patent Application Publication No. 0078991, European Patent Application Publication No. 0696606 and European Patent Application Publication No. 0807623.

[0019] Most preferably, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates having aliphatic, alicyclic, araliphatic and / or aromatically bonded isocyanate groups in the molecular weight range of 140 g / mol to 600 g / mol, examples of which include 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), as well as 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, and 1,5-diisocyanatonaphthalene (NDI).

[0020] Mixtures of two or more of the above polyisocyanate compounds (A) may also be used.

[0021] As used herein, the term "aliphatic polyisocyanate compound" is intended to denote a compound having two or more isocyanate groups and no aromatic moieties.

[0022] In a preferred embodiment of the process according to the invention, the polyisocyanate compound (A) is an aliphatic or cycloaliphatic polyisocyanate (A-1).

[0023] In one embodiment of the method according to the present invention, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from the group consisting of polyisocyanates having aliphatically or alicyclically bound isocyanate groups in the molecular weight range of 140 g / mol to 400 g / mol, examples of which include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, and the like. diisocyanatooctane, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,12-diisocyanatododecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-dicyclohexylpropane, 1-isocyanato-1-methyl-4(3)isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbornane, or any of the above-mentioned methods described, for example, in J. Prakt. Chem.336 (1994) 185-200, German Patent Application Publication No. 1670666, German Patent Application Publication No. 1954093, German Patent Application Publication No. 2414413, German Patent Application Publication No. 2452532, German Patent Application Publication No. 2641380, German Patent Application Publication No. 3700209, German Patent Application Publication No. 3900053 and German Patent Application Publication No. 3928503 or European Patent Application Publication No. 0336205, European Patent Application Publication No. 0339396 and any polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure, such as those of the types mentioned above, prepared by modification of simple aliphatic and / or cycloaliphatic diisocyanates, as described in EP-A-0 798 299, or a mixture of at least two such polyisocyanates.

[0024] More preferably, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from the group consisting of polyisocyanates having aliphatic, alicyclic, araliphatic and / or aromatically bonded isocyanate groups in a molecular weight range of 140 g / mol to 400 g / mol, examples of which include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2, 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-dicyclohexylpropane, or, for example, J. Prakt. Chem. 336 (1994) 185- 200, German Patent Application Publication No. 1670666, German Patent Application Publication No. 1954093, German Patent Application Publication No. 2414413, German Patent Application Publication No. 2452532, German Patent Application Publication No. 2641380, German Patent Application Publication No. 3700209, German Patent Application Publication No. 3900053, German Patent Application Publication No. 3928503, or European Patent Application Publication No. 0336205, European Patent Application Publication No. 0339396 and any polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure, such as those of the types mentioned above, prepared by modification of simple aliphatic and / or cycloaliphatic diisocyanates as described in EP-A-0 798 299, or a mixture of at least two such polyisocyanates.

[0025] Most preferably, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from the group consisting of 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), and 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI).

[0026] Mixtures of two or more of the above polyisocyanate compounds (A) may also be used.

[0027] As used herein, the term "aromatic polyisocyanate compound" is intended to refer to a compound having two or more isocyanate groups and an aromatic moiety.

[0028] In a less preferred embodiment of the process according to the invention, the polyisocyanate compound (A) is an aromatic and / or araliphatic polyisocyanate compound (A-2).

[0029] In a preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound selected from the group consisting of araliphatic and / or aromatic diisocyanates and triisocyanates in the molecular weight range of 160 g / mol to 600 g / mol, such as 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 1,3-bis(isocyanatomethyl ... )-4-methylbenzene, 1,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3-bis(isocyanatomethyl)-5-methylbenzene, 1,3-bis(isocyanatomethyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)-5-tert-butylbenzene, 1,4-bis(2-isocyanatomethyl) phenylene diisocyanate, 2,4-diisocyanatotoluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, diisopropylphenylene diisocyanate, diisododecylphenylene diisocyanate, and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'-, and 4,4'-Diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI), diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, triisocyanatobenzene, 2,4,6-triisocyanatotoluene, trimethylbenzene triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methyl naphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, as well as polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric MDI", and also those disclosed, for example, in DE-A-870400. , German Patent Application Publication No. 953012, German Patent Application Publication No. 1090196, European Patent Application Publication No. 0546399, Chinese Patent No. 105218780, Chinese Patent No. 103881050, Chinese Patent No. 101717571, U.S. Patent No. 3183112, European Patent Application Publication No. 0416338, European Patent Application Publication No. 0751163, European Patent Application Publication No. 1378529, European Patent Application Publication No. Polyisocyanates having a urethane and / or isocyanurate structure, which can be obtained by reaction of monomeric 2,4- and / or 2,6-TDI with polyols and / or oligomerization, preferably trimerization, which can be obtained by any known method, as described in JP-A-1378530, EP-A-2174967, JP-A-63-260915 or JP-A-56-059828, as well as polyisocyanate compounds having both aromatic and aliphatic isocyanate groups, such as the mixed trimers or allophanates of 2,4- and / or 2,6-TDI and HDI, as described in DE-A-1670667, EP-A-0078991, EP-A-0696606 and EP-A-0807623.

[0030] In a more preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound selected from the group consisting of araliphatic and / or aromatic diisocyanates and triisocyanates in the molecular weight range of 160 g / mol to 600 g / mol, such as 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 1,3-bis(isocyanatomethyl ... )-4-methylbenzene, 1,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3-bis(isocyanatomethyl)-5-methylbenzene, 1,3-bis(isocyanatomethyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)-5-tert-butylbenzene, 1,3-bis(isocyanatomethyl) 1,4-bis(isocyanatomethyl)-4-chlorobenzene, 1,3-bis(isocyanatomethyl)-4,5-dichlorobenzene, 1,3-bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromobenzene, 1,4-bis(2-isocyanatoethyl)benzene and 1,4-bis(isocyanatomethyl)naphthalene, 1,2-, 1,3- and 1,4-diisocyanatobenzene (phenylene diisocyanate), 2,4 - and 2,6-diisocyanatotoluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, isomeric diethylphenylene diisocyanates, diisopropylphenylene diisocyanate, diisododecylphenylene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-Diisocyanatodiphenylethane, 1,5-Diisocyanatonaphthalene (NDI), Diphenyl ether diisocyanate, Ethylene glycol diphenyl ether diisocyanate, Diethylene glycol diphenyl ether diisocyanate, 1,3-Propylene glycol diphenyl ether diisocyanate, Benzophenone diisocyanate, Triisocyanatobenzene, 2,4,6-Triisocyanatotoluene, Trimethylbenzene triisocyanate, Diphenylmethane-2,4,4'-triisocyanate, 3-Methyldiphen diisocyanatodiphenylmethane-4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methyl naphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'-pentaiisocyanate, as well as the polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric MDI", and also those disclosed, for example, in DE-A-870400, DE-A-953012, DE-A-953013, DE-A-953014, DE-A-953015, DE-A-953016, DE-A-953017, DE-A-953018, DE-A-953019 ... and the monomer 2,4-, which can be obtained by any known method, as described in JP-A-1090196, EP-A-0546399, CN-A-105218780, CN-A-103881050, CN-A-101717571, U.S. Pat. No. 3,183,112, EP-A-0416338, EP-A-0751163, EP-A-1378529, EP-A-1378530, EP-A-2174967, JP-A-63-260915 or JP-A-56-059828. and / or 2,6-TDI by reaction with polyols and / or oligomerization, preferably trimerization, and / or polyisocyanates having a urethane and / or isocyanurate structure, or mixtures of at least two such polyisocyanates, as well as polyisocyanate compounds having both aromatic and aliphatic isocyanate groups, such as the 2,4- and / or 2,6-TDIs described in DE-A-1 670 667, EP-A-0 078 991, EP-A-0 696 606 and EP-A-0 807 623.Selected from the group consisting of mixed trimers or allophanates of 6-TDI and HDI.

[0031] In the most preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound selected from the group consisting of 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI).

[0032] A mixture of two or more of the aromatic polyisocyanate compounds (A-2) can also be used.

[0033] As used herein, the term "polyepoxide compound" is intended to denote a compound having two or more epoxide groups.

[0034] In a preferred embodiment of the present invention, the polyepoxide compound (B) is an aliphatic or alicyclic polyepoxide compound (B-1) and / or an aromatic or araliphatic polyepoxide compound (B-2), preferably an aliphatic polyepoxide compound (B-1).

[0035] In a preferred embodiment of the present invention, the epoxide compound (B) is selected from the group consisting of resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tetrabromobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol F diglycidyl ether, tetramethylbisphenol S diglycidyl ether, diglycidyl terephthalate, diglycidyl-o-phthalate, trimellitic acid triglycidyl ester, 1,4-cyclohexanedicarboxylic acid diglycidyl ester, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl Glycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, polybutadiene diepoxide, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, polyglycidyl ether of ethoxylated trimethylolpropane, poly(tetramethylene oxide) diglycidyl ether, pentaerythritol polyglycidyl ether, vinylcyclohexene diepoxide, limonene diepoxide, doubly unsaturated fatty acid C1-C18 alkyl Diepoxides of esters, polyepoxides of doubly unsaturated ethoxylated fatty alcohols, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenyl diglycidyl ether and diglycidyl isophthalate, tetrabromobisphenol A diglycidyl ether, cardanol-based diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxybenzene diglycidyl ether, bis-(4-hydroxyphenyl)-1,At least one compound selected from the group consisting of 1-ethane diglycidyl ether, bis-(4-hydroxyphenyl)-1,1-isobutane diglycidyl ether, bis-(4-hydroxyphenyl)ether diglycidyl ether, and chlorinated and brominated versions of the aforementioned components.

[0036] Aliphatic diglycidyl ethers or polyglycidyl ethers obtained by epoxidation of difunctional or polyfunctional alcohols having an aliphatic linear, aliphatic branched, or alicyclic moiety consisting of 2 to 40 carbon atoms, such as ethanediol diglycidyl ether, propanediol diglycidyl ether, isosorbide diglycidyl ether, octanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyethylene triglycidyl ether, and 2-ethylhexyl diglycidyl ether.

[0037] More preferably, the polyepoxide compound (B) is selected from the group consisting of neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1,4-cyclohexanedicarboxylic acid diglycidyl ester, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, polyglycidyl ether of ethoxylated trimethylolpropane, poly(tetramethylene oxide) diglycidyl ether, pentaerythritol polyglycidyl ether, vinylcyclohexene diepoxide, diepoxide of doubly unsaturated fatty acid C1 to C18 alkyl ester, doubly unsaturated and aliphatic diglycidyl ethers or polyglycidyl ethers obtained by epoxidation of di- or polyfunctional alcohols having an aliphatic linear, aliphatic branched, or alicyclic moiety consisting of 2 to 40 carbon atoms, such as ethanediol diglycidyl ether, propanediol diglycidyl ether, isosorbide diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, octanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyethylene triglycidyl ether, 2-ethylhexyl diglycidyl ether, isosorbide diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether.

[0038] Most preferably, the polyepoxide compound (B) is selected from the group consisting of ethanediol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether.

[0039] Mixtures of two or more of the above polyepoxide compounds (B) may also be used.

[0040] As used herein, the term "aliphatic polyepoxide compound" is intended to denote a compound having two or more epoxide groups and also an aromatic moiety.

[0041] In a preferred embodiment of the present invention, the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0042] In a preferred embodiment of the present invention, the aliphatic polyepoxide compound (B-1) is one or more compounds, such as neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1,4-cyclohexanedicarboxylic acid diglycidyl ester, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, polyglycidyl ether of ethoxylated trimethylolpropane, poly(tetramethylene-oxide) diglycidyl ether, pentaerythritol polyglycidyl ether, vinylcyclohexene diepoxide, diepoxides of doubly unsaturated fatty acid C1-C18 alkyl esters, polyepoxides of doubly unsaturated ethoxylated fatty alcohols, aliphatic diglycidyl ethers or polyglycidyl ethers obtained by epoxidation of di- or polyfunctional alcohols having an aliphatic linear, aliphatic branched, or alicyclic moiety consisting of 2 to 40 carbon atoms, such as ethanediol diglycidyl ether, propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, octanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyethylene triglycidyl ether, 2-ethylhexyl diglycidyl ether, isosorbide diglycidyl ether.

[0043] In a more preferred embodiment of the present invention, the aliphatic polyepoxide compound (B-1) is one or more compounds, and is selected from the group consisting of hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol triglycidyl ether, polyglycidyl ether of ethoxylated trimethylolpropane, poly(tetramethylene-oxide) diglycidyl ether, pentaerythritol polyglycidyl ether, diepoxide of doubly unsaturated fatty acid C1-C18 alkyl ester, diepoxide of 2 to 40 alkyl esters ... aliphatic diglycidyl ethers or polyglycidyl ethers obtained by epoxidation of di- or polyfunctional alcohols having an aliphatic linear, aliphatic branched, or alicyclic moiety consisting of 10 carbon atoms, such as ethanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyethylene triglycidyl ether, 2-ethylhexyl diglycidyl ether, isosorbide diglycidyl ether.

[0044] Most preferably, the aliphatic polyepoxide compound (B-1) is one or more compounds selected from the group consisting of ethanediol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether.

[0045] Mixtures of two or more of the above-mentioned aliphatic polyepoxide compounds (B-1) can also be used.

[0046] As used herein, the term "aromatic polyepoxide compound" is intended to denote a compound having two or more epoxide groups and also an aromatic moiety.

[0047] In an alternative preferred embodiment of the present invention, the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0048] In a preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds, and is selected from the group consisting of resorcinol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tetrabromobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol F diglycidyl ether, tetramethylbisphenol S diglycidyl ether, diglycidyl terephthalate, diglycidyl-o-phthalate, trimellitic acid triglycidyl ester, 1,4-cyclohexyl methyl ester, and the like. The hydroxybenzoates are selected from the group consisting of bis(4-hydroxyphenyl)-1,1-ethane diglycidyl ether, bis(4-hydroxyphenyl)-1,1-isobutane diglycidyl ether, bis(4-hydroxyphenyl)ether diglycidyl ether, bis(4-hydroxyphenyl)ether diglycidyl ether, bis(4-hydroxyphenyl)ether diglycidyl ether, bis(4-hydroxyphenyl)ether diglycidyl ether, and chlorinated and brominated forms of the foregoing components.

[0049] In a more preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetramethyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetramethyl bisphenol S diglycidyl ether, diglycidyl terephthalate, diglycidyl-o-phthalate, 2-dihydroxybenzene diglycidyl ether, 1,4 ... diglycidyl isophthalate, cardanol-based diglycidyl ethers, hydroquinone diglycidyl ether, 4,4'-dihydroxyphenyl diglycidyl ether, bis-(4-hydroxyphenyl)-1,1-ethane diglycidyl ether, bis-(4-hydroxyphenyl)-1,1-isobutane diglycidyl ether, and bis-(4-hydroxyphenyl)ether diglycidyl ether.

[0050] In the most preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetramethyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetramethyl bisphenol S diglycidyl ether, diglycidyl terephthalate, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, and diglycidyl isophthalate.

[0051] Mixtures of two or more of the above aromatic polyepoxide compounds (B-2) can also be used.

[0052] In a first alternative preferred embodiment of the present invention, the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1), and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0053] In a second alternative preferred embodiment of the present invention, the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1), and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0054] In a third alternative preferred embodiment of the present invention, the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2), and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0055] In a fourth alternative preferred embodiment of the present invention, the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2), and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0056] A mixture of one or more of the above-mentioned aliphatic polyisocyanates (A-1), aromatic polyisocyanate compounds (A-2), aliphatic polyepoxide compounds (B-1) and / or aromatic polyepoxide compounds (B-2) can also be used.

[0057] In a preferred embodiment of the present invention, the molar ratio of the isocyanate groups of the polyisocyanate compound (A) to the epoxy groups of the polyepoxide compound (B) is 2.6:1 to 7:1, preferably 2.7:1 to 6:1, and more preferably 2.8:1 to 5:1. If the latter molar ratio exceeds 7:1 and an isocyanate-terminated oxazolidinone is obtained, the oxazolidinone groups of the entire mixture will be too diluted by the residual isocyanate monomer to affect the properties of the final polymer compared to a polymer polymerized from only the monomeric polyisocyanate compound.

[0058] In a preferred embodiment of the present invention, the method further comprises: i) mixing a polyisocyanate compound (A), a polyepoxide compound (B), a catalyst (C), and optionally a solvent (D) to form a mixture (i); ii) copolymerizing the mixture (i) to form an isocyanate-terminated polyoxazolidinone mixture (ii); iii) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (ii); Includes.

[0059] In an alternative preferred embodiment of the present invention, the method comprises: α) mixing the polyepoxide compound (B), at least a portion of the catalyst (C), and optionally at least a portion of the solvent (D) to form a mixture (α); β) adding a polyisocyanate compound (A) to the mixture (α) under copolymerization conditions to form an isocyanate-terminated polyoxazolidinone mixture (β); γ) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (β); Includes.

[0060] In a further alternative, less preferred embodiment of the present invention, the method further comprises: a) mixing the polyisocyanate compound (A), at least a portion of the catalyst (C), and at least a portion of the solvent (D) to form a mixture (a); b) adding a polyepoxide compound (B) to the mixture (a) under copolymerization conditions to form an isocyanate-terminated polyoxazolidinone mixture (b); c) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (b); Includes.

[0061] The conditions for the copolymerization process at elevated temperatures are described above. Appropriate purification methods, such as thin-film evaporation, can be applied to remove the solvent (D) and / or unreacted polyisocyanate compound (A) in step i), step γ), or step c). Removal of the solvent (D) and / or unreacted polyisocyanate compound (A) can be beneficial for future polymerization applications, since, for example, halogen-containing solvents and / or unreacted polyisocyanate compound (A) can interfere with these polymerization reactions and adversely affect the resulting polymerization product. Furthermore, removal of the solvent (D) and / or monomeric polyisocyanate compound (A) can significantly reduce the amount of harmful monomeric polyisocyanate compound (A) and solvent (D), resulting in a product with lower health risks. The remaining polyoxazolidinone prepolymer is not expected to pose a higher risk than other polyisocyanate prepolymers that have relatively high molecular weights, are solvent-free, and have low concentrations of monomeric polyisocyanate compounds.

[0062] In a preferred embodiment of the present invention, in order to remove the solvent (D) and / or the unreacted polyisocyanate compound (A), which may interfere with these polymerization reactions and have an adverse effect on the subsequent polymerization product, the unreacted polyisocyanate compound (A) and / or the solvent (D) are removed by distillation, preferably thin-film evaporation.

[0063] 2. The method according to claim 1, wherein the monomeric polyisocyanate compounds (A) and / or the solvent (D) are removed by a thermal treatment method, preferably by distillation and / or extraction, more preferably by thin film evaporation.

[0064] In a preferred embodiment of the present invention, the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, LiI, MgCl, MgBr, MgI, SmI, PhSbBr, PhSbCl, PhPBr, PhPCl, Ph(C6H4-OCH3)PBr, Ph(C6H4-OCH3)PCl, Ph(C6H4F)PCl and Ph(C6H4F)PBr, preferably LiCl, LiBr, LiI and MgCl.

[0065] In a more preferred embodiment of the present invention, the catalyst (C) is selected from the group consisting of LiCl, LiBr and LiI.

[0066] In a more preferred embodiment of the present invention, the catalyst (C) is LiBr.

[0067] In one embodiment of the process according to the invention, the catalyst (C) is present in a molar amount of 0.001 mol % to 2.0 mol %, preferably 0.01 mol % to 1.5 mol %, more preferably 0.05 mol % to 1.0 mol %, based on the polyepoxide compound (B).

[0068] In one embodiment of the present invention, a solvent (D) is used.

[0069] In one embodiment of the present invention, the calculated mass ratio of the total of the diisocyanate compound (A), the bisepoxide compound (B), and the catalyst (C) to the total of the diisocyanate compound (A), the bisepoxide compound (B), the catalyst (C), and the solvent (D) is in the range of 40 wt% to 100 wt%, preferably 50 wt% to 90 wt%, and more preferably 60 wt% to 80 wt%.

[0070] The solvent (D) is defined, in accordance with the general definition, as a substance that dissolves the solute, i.e., the compound (A) and / or the compound (B) and / or the compound (C), but does not (chemically) react with the compound (A), the compound (B) and / or the catalyst (C), in particular the polyisocyanate compound (A).

[0071] Suitable solvents (D) are, for example, linear or branched alkanes or mixtures of alkanes, toluene, xylene and mixtures of isomeric xylenes, mesitylene, mono- or poly-substituted halogenated aromatic solvents or halogenated alkane solvents, for example linear or cyclic ethers, linear or cyclic esters such as chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, tetrachloroethane, tetrahydrofuran (THF) or methyl tert-butyl ether (EMTBE), or polar aprotic solvents such as 1,4-dioxane, acetonitrile, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), etc. Solvents include cyclic carbonates such as ethylene carbonate or propylene carbonate, N-methylpyrrolidone (NMP), sulfolane, tetramethylurea, N,N'-dimethylethyleneurea, or mixtures of the above-mentioned solvents and / or other solvents, organic solvents such as 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, xylene, toluene, ethylene glycol ether, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, butylene glycol, butylene glycol monoalkyl ether, butylene glycol dialkyl ether, etc.

[0072] Preferred solvents (D) are 1,2-dichlorobenzene, sulfolane, N-methylpyrrolidone (NMP), ethyl acetate, butyl acetate, methoxypropyl acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, xylene, toluene, ethylene glycol dialkyl ether, and butylene glycol dialkyl ether.

[0073] Another aspect of the present invention is the isocyanate-terminated polyoxazolidinone obtainable by the process according to the present invention.

[0074] In one embodiment of the present invention, the polyoxazolidinone has an isocyanate equivalent weight (IEW) of 100 g / eq to 10,000 g / eq, preferably 150 g / eq to 6,000 g / eq, more preferably 200 g / eq to 2,000 g / eq, the isocyanate equivalent weight being determined by titration according to DIN EN ISO 11909:2007.

[0075] The isocyanate equivalent weight (IEW) of a polyoxazolidinone is defined as the total mass of material containing one equivalent of isocyanate groups.

[0076] In a first embodiment, the present invention provides a method for preparing an isocyanate-terminated polyoxazolidinone, comprising copolymerizing a polyisocyanate compound (A) having two or more isocyanate groups and a polyepoxide compound (B) having two or more epoxy groups in the presence of a catalyst (C), optionally in a solvent (D); the molar ratio of the isocyanate groups of the polyisocyanate compound (A) to the epoxy groups of the polyepoxide compound (B) is greater than 2:1 and less than 25:1; The catalyst (C) Li(I), Rb(I), Cs(I), Ag(I), Au(I), Mg(II), Ca(II), Sr(II), Ba(II), Dy(II), Cu(II), Zn(II), V(II), Mo(II), Mn(II), Fe(II), Co(II), Ni(II), Pd(II), Pt(II), Ge(II), Sn(II), Sc(III), Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Lu(III), Hf(III), Nb(III), Ta(III), Cr(III), Ru(III), Os(III), Rh(III), Ir(III), Al(III), Ga(III), In(III), Tl(III), Ge(III), Ce(IV), Ti(IV), Zr(IV), Hf(IV), Nb(IV), Mo(IV), W(IV), Ir(IV), Pt(IV), Sn(IV), Pb(IV), Nb(V), Ta(V), Bi(V), Mo(VI), W(VI), and Formula (I): [M(R1)(R2)(R3)(R4)]+n Yn- (I) wherein M is phosphorus or antimony, preferably phosphorus; (R1), (R2), (R3), and (R4) are each independently selected from the group consisting of a linear or branched alkyl group containing 1 to 22 carbon atoms, optionally substituted with a heteroatom and / or a heteroatom-containing substituent, an alicyclic group containing 3 to 22 carbon atoms, optionally substituted with a heteroatom and / or a heteroatom-containing substituent, a C1-C3 alkyl-bridged alicyclic group containing 3 to 22 carbon atoms, optionally substituted with a heteroatom and / or a heteroatom-containing substituent, and an aryl group containing 6 to 18 carbon atoms, optionally substituted with one or more alkyl groups and / or heteroatom-containing substituents and / or heteroatoms, each containing 1 to 10 carbon atoms; Y is a halide, carbonate, nitrate, sulfate or phosphate anion, more preferably a halide or carbonate anion; wherein n is an integer of 1, 2, or 3; wherein the compound is at least one compound selected from the group consisting of:

[0077] In a second embodiment, the present invention relates to the process according to the first embodiment, wherein the molar ratio of isocyanate groups of the polyisocyanate compound (A) to epoxy groups of the polyepoxide compound (B) is from 2.6:1 to 7:1, preferably from 2.7:1 to 6:1, more preferably from 2.8:1 to 5:1.

[0078] In a third embodiment, the present invention relates to the process according to the first or second embodiment, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1) and / or an aromatic polyisocyanate compound (A-2), preferably an aliphatic polyisocyanate compound (A-1).

[0079] In a fourth embodiment, the present invention relates to the process according to the second embodiment, wherein the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1) and / or an aromatic polyepoxide compound (B-2), preferably an aliphatic polyepoxide compound (B-1).

[0080] In a fifth embodiment, the present invention relates to a method according to any one of the first to fourth embodiments, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1) and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0081] In a sixth embodiment, the present invention relates to a method according to any one of the first to fourth embodiments, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1) and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0082] In a seventh embodiment, the present invention relates to a method according to any one of the first to fourth embodiments, wherein the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2) and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0083] In an eighth embodiment, the present invention relates to a method according to any one of the first to fourth embodiments, wherein the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2) and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0084] In a ninth embodiment, the present invention relates to a process according to any of the first to eighth embodiments, wherein the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, LiI, MgCl, MgBr, MgI, SmI, PhSbBr, PhSbCl, PhPBr, PhPCl, Ph(C6H4-OCH3)PBr, Ph(C6H4-OCH3)PCl, Ph(C6H4F)PCl and Ph(C6H4F)PBr, preferably LiCl, LiBr and LiI, most preferably LiBr.

[0085] In a tenth embodiment, the present invention relates to a process according to any of the first to ninth embodiments, wherein the catalyst (C) is used in a molar amount of 0.001 mol % to 2.0 mol %, preferably 0.01 mol % to 1.5 mol %, more preferably 0.05 mol % to 1.0 mol %, based on the polyepoxide compound (B).

[0086] In an eleventh embodiment, the present invention provides a method for manufacturing a semiconductor device, comprising: i) mixing a polyisocyanate compound (A), a polyepoxide compound (B), a catalyst (C), and optionally a solvent (D) to form a mixture (i); ii) copolymerizing the mixture (i) to form an isocyanate-terminated polyoxazolidinone mixture (ii); iii) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (ii); The present invention relates to a method according to any one of the first to tenth embodiments, including the method according to the first to tenth embodiments.

[0087] In a twelfth embodiment, the present invention provides a method for manufacturing a semiconductor device, comprising: α) mixing the polyepoxide compound (B), at least a portion of the catalyst (C), and at least a portion of the solvent (D) to form a mixture (α); β) adding the remaining portion of the polyisocyanate compound (A) and, optionally, the solvent (D) to the mixture (α) under copolymerization conditions to form an isocyanate-terminated polyoxazolidinone mixture (β); γ) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (β); The present invention relates to a method according to any one of the first to tenth embodiments, including the method according to the first to tenth embodiments.

[0088] In a thirteenth embodiment, the present invention relates to a method according to any of the first to twelfth embodiments, wherein the unreacted polyisocyanate compound (A) and / or the solvent (D) are removed by a thermal treatment method, preferably by distillation and / or extraction, more preferably by thin-film evaporation.

[0089] In a fourteenth embodiment, the present invention relates to an isocyanate-terminated polyoxazolidinone obtainable by the method according to any one of the first to thirteenth embodiments.

[0090] In a fifteenth embodiment, the present invention relates to an isocyanate-terminated polyoxazolidinone according to the fourteenth embodiment, having an isocyanate equivalent weight (IEW) of 100 g / eq to 10,000 g / eq, preferably 150 g / eq to 6,000 g / eq, more preferably 200 g / eq to 2,000 g / eq, wherein the epoxy equivalent weight is determined by titration according to DIN EN ISO 11909:2007.

[0091] In a sixteenth embodiment, the present invention provides a method for manufacturing a semiconductor device, comprising: a) mixing the polyisocyanate compound (A) and at least a portion of the catalyst (C), and optionally at least a portion of the solvent (D), to form a mixture (a); b) adding a polyepoxide compound (B) and optionally the remaining solvent (D) to the mixture (a) under copolymerization conditions to form an isocyanate-terminated polyoxazolidinone mixture (b); c) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (b); The present invention relates to a method according to any one of the first to tenth embodiments and the thirteenth embodiment, including the above. DETAILED DESCRIPTION OF THE INVENTION [Example]

[0092] The present invention will now be further described with reference to the following examples, without however wishing to be limited to these examples.

[0093] Diisocyanate compound (A) AI: 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (H 12 MDI), Covestro, AG (Germany).

[0094] Epoxide Compound (B) For the calculation of the experimental molar ratios, 100% compound purity was assumed for the diepoxide compounds. Possible impurities, such as alcohol compounds, were ignored in the calculations. BI: Araldite DY-D / CH butanediol diglycidyl ether (BDDE), EEW 118 g / eq to 125 g / eq; obtained from HUNTSMAN Advanced Materials (Deutschland) GmbH (Germany). Because Araldite DY-D / CH produces a significant amount of compounds that are not of the ideal structure (BDDE), the correction factor f for calculating the effective molar amount of epoxy groups was calculated based on the following formula: f(corrected) = (Mw(BDDE)(ideal structure)) / (EEW × functionality) = (202.25 g / mol) / (121 × 2) = 0.835 B-II: Denacol EX-810 1,2-ethanediol diglycidyl ether, EEW 113 g / eq, was obtained from NAGASE (Europa) GmbH (Germany). Because Araldite DY-D / CH produces a significant amount of compounds that are not of the ideal structure (BDDE), the correction factor f for calculating the effective molar amount of epoxy groups was calculated based on the following formula: f(corrected) = (Mw(BDDE)(ideal structure)) / (EEW × functionality) = (174.2 g / mol) / (113 × 2) = 0.770 B-III: Denacol EX-212 1,6-hexanediol diglycidyl ether, EEW 151 g / eq, was obtained from NAGASE (Europa) GmbH (Germany). Because Araldite DY-D / CH produces a significant amount of compounds that are not of the ideal structure (BDDE), the correction factor f for calculating the effective molar amount of epoxy groups was calculated based on the following formula: f(corrected) = (Mw(BDDE)(ideal structure)) / (EEW × functionality) = (230.3 g / mol) / (151 × 2) = 0.720

[0095] Catalyst (C) CI:LiCl Lithium chloride, >99% purity was obtained from Sigma Aldrich. C-II:DABCO 1,4-diazabicyclo[2.2.2]octane, >99% purity was obtained from Sigma Aldrich. C-III: LiBr Lithium bromide, purity >99.995%, was obtained from Sigma Aldrich. C-IV:Yb(OTf)3 ytterbium tris(trifluoromethanesulfonate), 99%, was obtained from Sigma Aldrich.

[0096] Catalyst concentrations are given in equivalents relative to the molar amount of isocyanate component, and unless otherwise stated, the catalyst concentration is 0.07 eq.

[0097] Solvent (D) DI: ortho-dichlorobenzene (o-DCB), 99% purity, anhydrous, was obtained from Sigma-Aldrich (Germany). D-II: Sulfolane, purity ≥99%, anhydrous, was obtained from Sigma-Aldrich (Germany).

[0098] H 12 MDI, LiCl, and epoxide compounds were used as received without further purification. Sulfolane was melted at 50°C and dried over molecular sieves before use. o-DCB was dried over molecular sieves before use.

[0099] Characterization of polyoxazolidinone prepolymers IR IR analysis was performed on a Bruker ALPHA-P IR spectrometer equipped with a diamond probe head. The software OPUS 6.5 was used for data processing. Background spectra were recorded against ambient air. A small sample (2 mg) of polyoxazolidinone prepolymer was then applied to the diamond probe and measured at a 4 cm -1 At a resolution of 4000 cm -1 ~400cm -1 The IR spectrum was recorded by averaging 24 spectra obtained in the range of .

[0100] The peak height ratio of oxazolidinone to isocyanurate was calculated using the formula: Ratio (oxazolidinone:isocyanurate) = (peak height (oxazolidinone)) / (peak height (isocyanurate)) (1) and for oxazolidinone at 1749 cm -1 Peak height of the peak at 1680 cm for isocyanurate -1 The peak height was calculated using the

[0101] Isocyanate Equivalent The isocyanate content was determined by titration according to DIN EN ISO 11909:2007.

[0102] color index The Gardner color index was determined using a Hach Lico 690. Therefore, samples of the product mixture were filled into cuvettes, which were subsequently analyzed according to DIN EN ISO 1557:1997.

[0103] Viscosity measurement Viscosity values were determined using an Anton Paar MCR 302 cone / plate rheometer. A shear rate ramp ranging from 10 1 / min to 600 1 / min was used to determine the viscosity of the products. Viscosity is reported in mPa·s (following a procedure in accordance with DIN EN ISO 3219 / A.3:1994). All measurements were performed at 23°C unless otherwise specified.

[0104] GPC GPC measurements were performed in tetrahydrofuran (THF, 1.0 mL / min flow rate) at 40°C. The column set consisted of four consecutive columns (two PSS SDV 50A, 5 μL, and two PSS SDV 100A, 5 μL). Samples (concentrations of 2 g / L to 3 g / L, injection volume 100 μL) were injected. The concentrations were monitored at the column outlet using an Agilent 1200 Series RID detector. Raw data were processed using PSS's WinGPC Unity software package. Polystyrenes of known molecular weights were used as references to calculate molecular weight distributions (PSS's ReadyCal kit was used in the range of 266 Da to 66,000 Da). The number average molecular weights measured by GPC are shown in the examples as M n (GPC).

[0105] reactor The reaction was carried out in a 250 mL four-neck round-bottom flask equipped with a glass reflux condenser, a gas inlet (N), a syringe pump (SyrDos IP-SYRDOS2-HP-XLP), a glass inlet tube equipped with a temperature probe (Ebro GFX 460), and an overhead KPG stirrer (IKA RW20). The round-bottom flask was heated with a Winkler heating mantle (WM / BRI / 250 with a maximum heating capacity of 120 W) connected to a temperature probe via an Ebro RB 1691 BS.

[0106] Example 1: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.2:1 12 Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Araldite DY-D / CH as compound (BI), LiCl(CI) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reactor was charged with LiCl (1.11 g, 0.26 mmol) (CI). Sulfolane (9.0 mL) (D-II) was then added, and the mixture was stirred (400 rpm) and flushed with nitrogen (approximately 1 mL / min) for 30 minutes. The mixture was then heated to 175 °C, and o-DCB(DI) (17 mL) was added. Araldite DY-D / CH (17.44 g, 0.072 mol) (BI), H 12 A mixture of MDI (98.38 g, 0.38 mol) (AI) and o-DCB (11 mL) (D-1) was added continuously via a syringe pump at a rate of 4.2 mL / min. After the monomer addition was complete, the reaction was stirred and heated for an additional 210 min, after which the reaction mixture was cooled to room temperature.

[0107] Samples of the reaction mixture were taken during the course of the reaction and analyzed by IR spectroscopy. The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture was -1 Completion of the reaction was confirmed by observing that the epoxide band no longer changed. Unfortunately, the epoxide band cannot be distinguished from noise signals.

[0108] In the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group is at 1749 cm -1 was observed.

[0109] In the IR spectrum, characteristic signals of isocyanurate groups were observed. The peak height ratio was calculated according to equation (1). A value of 3.73 was determined for the product mixture.

[0110] The isocyanate equivalent weight was determined to be 291 g / eq.

[0111] Molecular weight analysis using GPC showed an average molecular weight of 486 g / mol and a polydispersity index of 2.8.

[0112] The viscosity of the product mixture was determined to be 530 mPa·s.

[0113] According to the Gardner scale, the color index of the product mixture was determined to be 5.1.

[0114] Example 2: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.2:1 12 Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Araldite DY-D / CH as compound (BI), DABCO (C-II) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 1, except that DABCO(C-II) was used as the catalyst instead of LiCl(CI).

[0115] The peak height ratio of oxazolidinone to isocyanurate was calculated as described in equation (1). A value of 0.78 was determined for the product mixture. Additionally, various by-products can be observed in the IR spectrum.

[0116] The isocyanate equivalent weight was determined to be 371 g / eq.

[0117] Molecular weight analysis using GPC showed an average molecular weight of 584 g / mol with a polydispersity index of 5.76.

[0118] The product mixture has a viscosity of 14300 mPa·s.

[0119] According to the Gardner scale, the color index of the product mixture was above the detection limit of 18 (>18) due to the color being too intense.

[0120] Example 3: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.6:1 12 Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Denacol EX-810 as compound (B-II), LiCl(CI) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 1, except that Denacol EX-810 (B-II) (15.2 g, 0.053 mol) was used instead of Araldite DY-D / CH (BI).

[0121] The oxazolidinone to isocyanurate peak height ratio was calculated as described in equation (1). A value of 6.6 was determined for the product mixture.

[0122] The isocyanate equivalent weight was determined to be 270 g / eq.

[0123] Molecular weight analysis using GPC showed an average molecular weight of 342 g / mol with a polydispersity index of 2.83.

[0124] The product mixture has a viscosity of 204 mPa·s.

[0125] According to the Gardner scale, the color index of the product mixture was determined to be 4.8.

[0126] Example 4: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 1:3.2 12 Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Denacol EX-810 as compound (B-II), LiCl(CI) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 4, except that H 12 The monomer ratio of MDI (AI) to Denacol EX-810 (B-II) (26.1 g, 0.092 mol) was changed from 5.6:1 to 3.2:1.

[0127] The oxazolidinone to isocyanurate peak height ratio was calculated as described in equation (1). A value of 4.83 was determined for the product mixture.

[0128] The isocyanate equivalent weight was determined to be 358 g / eq.

[0129] Molecular weight analysis using GPC showed an average molecular weight of 586 g / mol with a polydispersity index of 3.14.

[0130] The product mixture has a viscosity of 19700 mPa·s.

[0131] According to the Gardner scale, the color index of the product mixture was determined to be 11.0.

[0132] Example 5: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.9:1 12Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Denacol EX-212 as compound (B-III), LiCl(CI) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 1, except that Denacol EX-212 (B-III) (19.9 g, 0.05 mol) was used instead of Araldite DY-D / CH(BI).

[0133] The oxazolidinone to isocyanurate peak height ratio was calculated as described in equation (1). A value of 5.21 was determined for the product mixture.

[0134] The isocyanate equivalent weight was determined to be 376 g / eq.

[0135] Molecular weight analysis using GPC showed an average molecular weight of 376 g / mol with a polydispersity index of 2.38.

[0136] The product mixture has a viscosity of 239 mPa·s.

[0137] According to the Gardner scale, the color index of the product mixture was determined to be 3.4.

[0138] Monomer H 12 The MDI and solvent mixture was removed in a thin film evaporator at a temperature of 180° C. and a pressure of 0.1 mbar. This gave a light brown solid product with an isocyanate equivalent weight of 700 g / eq and 0.8% of monomer H 12 The content of MDI was determined by GPC measurement.

[0139] Example 6: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.2:1 12Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Araldite DY-D / CH as compound (BI), LiCl(CI) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 1, except that less LiCl(Cl) was used (0.01 eq instead of 0.07 eq).

[0140] The oxazolidinone to isocyanurate peak height ratio was calculated as described in equation (1). A value of 6.05 was determined for the product mixture.

[0141] The isocyanate equivalent weight was determined to be 277 g / eq.

[0142] Molecular weight analysis using GPC showed an average molecular weight of 449 g / mol with a polydispersity index of 2.36.

[0143] The product mixture has a viscosity of 529 mPa·s.

[0144] According to the Gardner scale, the color index of the product mixture was determined to be 5.8.

[0145] Example 7: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.2:1 12 Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Araldite DY-D / CH as compound (BI), LiBr (C-III) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 7, except that LiBr(C-III) was used instead of LiCl(CI).

[0146] The oxazolidinone to isocyanurate peak height ratio was calculated as described in equation (1). A value of 14.4 was determined for the product mixture.

[0147] The isocyanate equivalent weight was determined to be 277 g / eq.

[0148] Molecular weight analysis using GPC showed an average molecular weight of 450 g / mol with a polydispersity index of 2.24.

[0149] The product mixture has a viscosity of 480 mPa·s.

[0150] According to the Gardner scale, the color index of the product mixture was determined to be 5.8.

[0151] Example 8: H as compound (AI) in a semi-batch procedure with a molar ratio of isocyanate groups to epoxy groups of 5.2:1 12 Synthesis of isocyanate-terminated polyoxazolidinone-based prepolymers using MDI, Araldite DY-D / CH as compound (BI), Yb(OTf)3 (C-III) as compound (C), and a solvent mixture containing o-DCB as compound (DI) and sulfolane as compound (D-II). The reaction was carried out in the same manner as described for Example 7, except that Yb(OTf)3(C-IV) was used instead of LiCl(CI).

[0152] The oxazolidinone to isocyanurate peak height ratio was calculated as described in equation (1). A value of 1.45 was determined for the product mixture.

[0153] The isocyanate equivalent weight was determined to be 287 g / eq.

[0154] Molecular weight analysis using GPC showed an average molecular weight of 643 g / mol with a polydispersity index of 6.24.

[0155] The product mixture has a viscosity of 4200 mPa·s.

[0156] According to the Gardner scale, the color index of the product mixture was determined to be greater than 18.

[0157] comparison

[0158] [Table 1]

Claims

1. A method for producing an isocyanate-terminated polyoxazolidinone, comprising copolymerizing a polyisocyanate compound (A) having two or more isocyanate groups and a polyepoxide compound (B) having two or more epoxy groups in a solvent (D) in the presence of a catalyst (C), the molar ratio of the isocyanate groups of the polyisocyanate compound (A) to the epoxy groups of the polyepoxide compound (B) is 2.6:1 to 7:1; The catalyst (C) is LiCl, LiBr, LiI, Ph ４ PBr, Ph ４ PCl, Ph ３ (C ６ H ４ -OCH ３ ) PBr, Ph ３ (C ６ H ４ -OCH ３ ) PCl, Ph ３ (C ６ H ４ F) PCl and Ph ３ (C ６ H ４ F) at least one compound selected from the group consisting of PBr, The method, wherein the catalyst (C) is used in a molar amount of 0.001 mol % to 2.0 mol % based on the polyepoxide compound (B).

2. The method according to claim 1, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1) and / or an aromatic polyisocyanate compound (A-2).

3. 3. The method according to claim 1, wherein the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1) and / or an aromatic polyepoxide compound (B-2).

4. The method according to any one of claims 1 to 3, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1), and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

5. The method according to any one of claims 1 to 3, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1), and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

6. The method according to any one of claims 1 to 3, wherein the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2), and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

7. The method according to any one of claims 1 to 3, wherein the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2), and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

8. The method according to any one of claims 1 to 7, wherein the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, and LiI.

9. 9. The method according to claim 1, wherein the catalyst (C) is used in an amount of 0.01 mol % to 1.5 mol % based on the polyepoxide compound (B).

10. i) mixing the polyisocyanate compound (A), the polyepoxide compound (B), the catalyst (C), and the solvent (D) to form a mixture (i); ii) copolymerizing the mixture (i) to form an isocyanate-terminated polyoxazolidinone mixture (ii); iii) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (ii); The method according to any one of claims 1 to 9, comprising:

11. α) mixing the polyepoxide compound (B), at least a portion of the catalyst (C), and at least a portion of the solvent (D) to form a mixture (α); β) adding the polyisocyanate compound (A) and the remaining portion of the solvent (D) to the mixture (α) under copolymerization conditions to form an isocyanate group-terminated polyoxazolidinone mixture (β); γ) optionally removing the solvent (D) and / or unreacted polyisocyanate compound (A) from the isocyanate group-terminated polyoxazolidinone mixture (β); The method according to any one of claims 1 to 9, comprising:

12. The method according to any one of claims 1 to 11, wherein the unreacted polyisocyanate compound (A) and / or the solvent (D) are removed by a heat treatment method.

13. An isocyanate-terminated polyoxazolidinone obtainable by the method according to any one of claims 1 to 12.

14. 14. The isocyanate-terminated polyoxazolidinone according to claim 13, having an isocyanate equivalent weight of 100 g / eq to 10,000 g / eq, the isocyanate equivalent weight being determined by titration in accordance with DIN EN ISO 11909:2007.

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