Method for producing epoxy-terminated polyoxazolidinone

Abstract

The present invention relates to a method for producing an epoxy-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 epoxy groups of the polyepoxide compound (B) to the isocyanate groups of the polyisocyanate compound (A) is from 2.6:1 to less than 25:1, and the copolymerization is carried out at 1 bar (absolute) in the absence of an additional solvent (D-1) having a boiling point above 170°C, preferably above 165°C, more preferably above 160°C, and most preferably above 150°C. The present invention also relates to the resulting epoxy-terminated polyoxazolidinone.

Description

[Technical field]

[0001] The present invention relates to a method for producing an epoxy-terminated polyoxazolidinone, which comprises 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 specific catalyst (C), in which the molar ratio of the epoxy groups of the polyepoxide compound (B) to the isocyanate groups of the polyisocyanate compound (A) is from 2.6:1 to less than 25:1, and the copolymerization is carried out at 1 bar (absolute) in the absence of an additional solvent (D-1) having a boiling point above 170°C, preferably above 165°C, more preferably above 160°C, and most preferably above 150°C. The present invention also relates to the resulting epoxy-terminated polyoxazolidinones. [Background technology]

[0002] Oxazolidinones are structural motifs widely used in pharmaceutical applications, and 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 low chemoselectivity are common (Non-Patent Document 1). These disadvantages have led to a need for alternative methods to prepare oxazolidinones, especially for the application of oxazolidinones 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 discloses a powder coating composition containing an epoxy-terminated polyoxazolidinone prepared by reacting a diepoxide with a diisocyanate, the ratio of epoxide equivalents to isocyanate equivalents being in the range of 10:1 to 1.1:1. The resulting polyoxazolidinone has an epoxy equivalent of 250 to 4000. In Example 1, an epoxy-terminated polyoxazolidinone powder is prepared in a first step by reacting toluene diisocyanate with a stoichiometric excess of ethanol in the presence of dibutyltin dilaurate to form a urethane, which is then reacted with an epoxide in the presence of triethyldiamine to form an oxazolidinone. In Examples 2 and 3, epoxy-terminated polyoxyazolidinone powders with epoxide equivalents to isocyanate equivalents of 1.6 and 1.96 were synthesized in the presence of tetraethylammonium bromide catalyst.

[0005] Patent Document 2 describes an oxazolidinone ring-containing epoxy resin, which is prepared by first reacting a diisocyanate with an alcohol to obtain a blocked polyurethane diisocyanate, which is then reacted with a diepoxide, and this reaction can proceed in the presence of a tertiary amine catalyst and, optionally, a tin cocatalyst.

[0006] US Patent No. 5,399,633 provides a method for preparing oligomeric oxazolidinone-containing polyepoxides based on bisepoxides and diisocyanates in the presence of phosphonium carboxylates or halides as a catalytic system. In the disclosed examples, the ratio of NCO groups of the applied diisocyanate to epoxy groups of the applied bisepoxide is between 1:1.6 and 1:2.0, resulting in solid polyoxazolidinones with epoxy equivalents of 460-711.

[0007] In Non-Patent Document 3, 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 to form oxazolidinones was investigated, where a molar ratio of BADGE to MDI up to 3 to 1 was applied. However, a significant amount of a by-product, namely isocyanurate, was detected.

[0008] Patent Document 4 discloses a method for producing an oxazolidinone compound, which comprises reacting an isocyanate composition containing at least one isocyanate compound with an epoxide composition containing an epoxide compound, using a polymetal cyanide compound as a catalyst, and applying the catalyst at a low catalyst concentration of 28 ppm to 34 ppm. The resulting oxazolidinone compound has an isocyanate peak at 1750 cm -1 The compound has a signal characteristic of the oxazolidinone carbonyl group at about 1725 cm -1 A signal can also be detected at 100° C., which is assigned to the by-product urethane carbonyl moiety. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent Application Publication No. 0113575 [Patent Document 2] US Patent Application Publication No. 2002 / 0037975 [Patent Document 3] DE 3720759 [Patent Document 4] International Publication No. 2019 / 081210 [Non-patent literature]

[0010] [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] Pelzer et al. (European Polymer Journal 107 (2018)) Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, the object of the present invention was to identify a simple one-step process for the preparation of epoxy-terminated polyoxazolidinones with a defined epoxy equivalent weight, preferably in combination with low polydispersity and reduced viscosity, for further polymerization applications.In this connection, it is necessary to reduce or avoid side reactions, such as those due to the formation of isocyanurates or polyurethanes.In addition, it is desirable to avoid the use of high-boiling solvents, which are commonly applied in oxazolidinone synthesis and need to be removed at high temperatures, in order to reduce the number of by-products, obtain oxazolidinones with less color, and result in a more energy-efficient process. [Means for solving the problem]

[0012] Surprisingly, the problem is a method for producing an epoxy-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), the molar ratio of the epoxy group of the polyepoxide compound (B) to the isocyanate group of the polyisocyanate compound (A) is from 2.6:1 to 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), Yb(II), Cu(II), V(II), Mo(II), Mn(II), Fe(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), Yb(I II), 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), (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 containing 1 to 10 carbon atoms and / or heteroatom-containing substituents and / or heteroatoms; Y is a halide, carbonate, nitrate, sulfate or phosphate anion, more preferably a halide or carbonate anion; n is an integer of 1, 2 or 3, At least one compound selected from the group consisting of It has been found that this problem can be solved by a process in which the copolymerization is carried out at 1 bar (absolute) in the absence of an additional solvent (D-1) having a boiling point above 170°C, preferably above 165°C, more preferably above 160°C, most preferably above 150°C.

[0013] As used herein, the term "polyoxazolidinone" is intended to denote a compound containing at least two oxazolidinone groups in the molecule. The term "epoxy group-terminated" polyoxazolidinone refers to a polyoxazolidinone compound from which the molar ratio of epoxy groups of the polyepoxide compound (B) to isocyanate groups of the polyisocyanate compound (A) is 2.6:1, and no terminal isocyanate groups are present in the polyoxazolidinone compound according to the invention.

[0014] In one embodiment of the method according to the invention, the copolymerization process is carried out at a reaction temperature of ≧130° C. to ≦280° C., preferably at a temperature of ≧140° C. to ≦240° C., more preferably at a temperature of ≧155° C. to ≦210° C., most preferably at a temperature of ≧165° C. to ≦195° C. If a temperature below 130° C. is set, the reaction generally becomes very slow. At temperatures above 280° C., the amount of undesirable secondary products increases significantly.

[0015] As used herein, the term "polyisocyanate compound" is intended to denote a compound having two or more isocyanate groups.

[0016] 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 aromatic and / or araliphatic polyisocyanate compound (A-2).

[0017] In one embodiment of the process according to the invention, the polyisocyanate compound (A) is at least one polyisocyanate which is accessible in various ways, for example by phosgenation in the liquid or gas phase or by phosgene-free routes, for example by thermal urethane cleavage.

[0018] 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 bonded isocyanate groups in the molecular weight range of 140 g / mol to 600 g / mol, examples of which are 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- ... 2,2,4- 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-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 in 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 prepared by modification of aromatic and / or cycloaliphatic diisocyanates, such as those of the types mentioned above, or a mixture 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-isocyanatopropanediisocyanate, XDI), 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)-2,3,5,6-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-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, the 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 diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'-Pentaiisocyanate, furthermore the polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric-MDI", ... No. 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 urethane and / or isocyanurate structures, obtainable from the monomers 2,4- and / or 2,6-TDI by reaction with polyols and / or oligomerization, preferably trimerization, obtainable by any of the known methods described, or mixtures of at least two such polyisocyanates, and also polyisocyanate compounds having both aromatic and aliphatic isocyanate groups, such as the mixed trimers or allophanates of 2,4- and / or 2,6-TDI with HDI, as described, for example, in DE-A-1 670 667, EP-A-0 078 991, EP-A-0 696 606 and EP-A-0 807 623.

[0019] More preferably, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates having aliphatic, alicyclic, araliphatic and / or aromatic bonded 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), 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 types mentioned 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 methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-Diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, as well as the polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric-MDI", as well as those described in, for example, DE 870400, DE 953012, DE 1090196, EP 0546399, CN 105218780, CN 103881050, CN 101717571, U.S. Pat. No. 3,183112, EP 0416338, EP 0751163, EP 1378529, EP 1378530, EP 2174967, JP 2003-113666, and US Pat. No. 5,233,663. Polyisocyanates having urethane and / or isocyanurate structures which can be obtained from the monomers 2,4- and / or 2,6-TDI by reaction with polyols and / or oligomerization, preferably trimerization, which can be obtained by any of the known methods described in JP-A-63-260915 or JP-A-56-059828, as well as polyisocyanate compounds which have both aromatic and aliphatic isocyanate groups, such as the mixed trimers or allophanates of 2,4- and / or 2,6-TDI with HDI, as described in DE-A-1 670 667, EP-A-0 078 991, EP-A-0 696 606 and EP-A-0 807 623.

[0020] Most preferably, the polyisocyanate compound (A) is 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), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), and 1,3- and 1,4-bis(isocyanatomethyl)benzene. and at least one compound selected from the group consisting of 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).

[0021] Mixtures of two or more of the abovementioned polyisocyanate compounds (A) may also be used.

[0022] As used herein, the term "aromatic polyisocyanate compound" is intended to denote a compound having two or more isocyanate groups and an aromatic moiety.

[0023] In a more preferred embodiment of the process according to the invention, the polyisocyanate compound (A) is an aromatic and / or araliphatic polyisocyanate compound (A-2).

[0024] In a preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound, which is selected from 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)- 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, 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 diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, as well as the polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric-MDI", as described, 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 urethane and / or isocyanurate structures obtainable from monomeric 2,4- and / or 2,6-TDI by reaction with polyols and / or oligomerization, preferably trimerization, obtainable by any of the known methods described in DE-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 described, for example, in DE-A-1670667, EP-A-0078991, EP-A-0696606 and EP-A-0807623.

[0025] In a more preferred embodiment of the method according to the present invention, the aromatic polyisocyanate compound (A-2) is at least one compound, which is selected from 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) 1,3-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-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, the 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 methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'-pentaisocyanate, as well as the polynuclear homologues of diisocyanatodiphenylmethane known as "polymeric-MDI", as well as the polyisocyanatodiphenylmethanes disclosed in, for example, DE-A-870400, DE-A-953012, DE-A-2000-1 ... 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-TDI described, for example, 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.

[0026] In the most preferred embodiment of the process 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).

[0027] Mixtures of two or more of the aromatic polyisocyanate compounds (A-2) can also be used.

[0028] As used herein, the term "aliphatic polyisocyanate compound" is intended to denote a compound having two or more isocyanate groups and no aromatic moieties.

[0029] In a less preferred embodiment of the process according to the invention, the polyisocyanate compound (A) is an aliphatic or cycloaliphatic polyisocyanate (A-1).

[0030] 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 bonded 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-diisocyanatohexa ... 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 methods described in, 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 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.

[0031] 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 aromatic bonded 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), 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 and German Patent Application Publication No. 3928503 or European Patent Application Publication No. 0336205, European Patent Application Publication No. 0339396 and any polyisocyanate having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures prepared by modification of simple aliphatic and / or cycloaliphatic diisocyanates as described in EP-A-0 798 299, such as those of the types mentioned above, or a mixture of at least two such polyisocyanates.

[0032] 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), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI).

[0033] Mixtures of two or more of the abovementioned polyisocyanate compounds (A-1) may also be used.

[0034] As used herein, the term "polyepoxide compound" is intended to denote a compound having two or more epoxide groups.

[0035] In a preferred embodiment of the present invention, 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).

[0036] 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 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 dihydroxyphenyl 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 ethers, 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 the chlorinated and brominated versions of the aforementioned components.

[0037] 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, octanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyethylene triglycidyl ether, 2-ethylhexyl diglycidyl ether.

[0038] 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, and diepoxy groups of doubly unsaturated fatty acid C1-C18 alkyl esters. aliphatic diglycidyl ethers or polydiglycidyl 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, bisphenol A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S diglycidyl ether.

[0039] 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.

[0040] Mixtures of two or more of the abovementioned polyepoxide compounds (B) may also be used.

[0041] 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.

[0042] In a preferred embodiment of the present invention, the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0043] 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 polydiglycidyl 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.

[0044] 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, 2 to 40 alkyl esters of 2 to 40 alkyl esters of 1 to 18 alkyl esters of 1 to 2 ... aliphatic diglycidyl ethers or polydiglycidyl ethers obtained by epoxidation of di- or polyfunctional alcohols having an aliphatic linear, aliphatic branched or alicyclic moiety consisting of carbon atoms of 1 to 4 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.

[0045] 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.

[0046] Mixtures of two or more of the above-mentioned aliphatic polyepoxide compounds (B-1) can also be used.

[0047] 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.

[0048] In an alternative preferred embodiment of the present invention, the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0049] 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-cyclo The diglycidyl ether is selected from the group consisting of hexanedicarboxylic acid diglycidyl ester, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenyl diglycidyl ether, diglycidyl isophthalate, tetrabromobisphenol A, 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, bis-(4-hydroxyphenyl)ether diglycidyl ether, and chlorinated and brominated versions of the above mentioned components.

[0050] 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.

[0051] 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, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, diglycidyl isophthalate, cardanol-based diglycidyl ethers, hydroquinone diglycidyl ether, and 4,4'-dihydroxyphenyl diglycidyl ether.

[0052] 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, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, and diglycidyl isophthalate. A mixture of two or more of the above aromatic polyepoxide compounds (B-2) can also be used.

[0053] 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).

[0054] 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).

[0055] 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).

[0056] 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).

[0057] Mixtures 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.

[0058] In a preferred embodiment of the present invention, the molar ratio of epoxy groups of the polyepoxide compound (B) to isocyanate groups of the polyisocyanate compound (A) 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. If the latter molar ratio exceeds 7:1 and an epoxy-terminated oxazolidinone is obtained, the mixture will not provide any significant benefit in the final polymer compared to using only the epoxy compound (B) for further polymerization applications, since the proportion of oxazolidinone groups in the entire mixture is diluted by the epoxy compound (B).

[0059] In a preferred embodiment of the invention, the method further comprises the steps of: i) mixing a polyisocyanate compound (A), a polyepoxide compound (B), and a catalyst (C) to form a mixture (i); ii) copolymerizing mixture (i); Includes.

[0060] In an alternative preferred embodiment of the invention, the method comprises the steps of: α) mixing at least a portion of the polyepoxide compound (B) and the catalyst (C) to form a mixture (α); β) adding a polyisocyanate compound (A) to the mixture (α) under copolymerization conditions; Includes.

[0061] In a further alternative, less preferred embodiment of the present invention, the method further comprises: γ) mixing at least a portion of the polyisocyanate compound (A) and the catalyst (C) to form a mixture (γ); δ) adding a polyepoxide compound (B) to the mixture (γ) under copolymerization conditions; Includes.

[0062] The high temperature copolymerization process conditions and temperatures are described above.

[0063] In a preferred embodiment of the invention, the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, LiI, MgCl2, MgBr2, MgI2, SmI3, Ph4SbBr, Ph4SbCl, Ph4PBr, Ph4PCl, Ph3(C6H4-OCH3)PBr, Ph3(C6H4-OCH3)PCl, Ph3(C6H4F)PCl and Ph3(C6H4F)PBr, preferably LiCl, LiBr, LiI and MgCl2.

[0064] In a more preferred embodiment of the invention, the catalyst (C) is selected from the group consisting of LiCl, LiBr and LiI.

[0065] In a more preferred embodiment of the present invention, the catalyst (C) is LiCl.

[0066] 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).

[0067] The solvent (D), in particular the solvent (D-1), is defined in accordance with the general definition as a substance that dissolves the solutes, i.e. the compound (A), the compound (B) and / or the compound (C), but does not (chemically) react with the compound (A), the compound (B) and the catalyst (C), in particular the polyisocyanate compound (A).

[0068] According to the process of the present invention, the copolymerization is carried out at 1 bar (absolute) in the absence of additional solvent (D-1) having a boiling point above 170°C, preferably above 165°C, more preferably above 160°C, most preferably above 150°C.

[0069] By in the absence of additional solvent (D-1) is meant a solvent amount of (D-1) of less than 5 wt%, preferably 4 wt%, more preferably less than 2 wt%.

[0070] These additional solvents (D-1) are, for example, organic solvents, such as linear or branched alkanes or mixtures of alkanes, mono- or poly-substituted halogenated aromatic solvents or halogenated alkane solvents, such as 1,2-dichlorobenzene, linear or cyclic esters, or polar aprotic solvents, such as cyclic carbonates, such as ethylene carbonate or propylene carbonate, N-methylpyrrolidone (NMP), sulfolane, tetramethylurea, N,N'-dimethylethyleneurea, or mixtures of the abovementioned solvents and / or mixtures with other solvents. These solvents (D-1) are in particular 1,2-dichlorobenzene, sulfolane and N-methylpyrrolidone (NMP).

[0071] In a preferred embodiment of the present invention, the copolymerization is carried out in the absence of additional solvent (D), which is an advantage since no additional energy-intensive and time-consuming solvent removal processes, such as distillation, are required.

[0072] In one embodiment of the present invention, the calculated mass ratio of the sum of the diisocyanate compound (A), the bisepoxide compound (B) and the catalyst (C) to the sum of the diisocyanate compound (A), the bisepoxide compound (B), the catalyst (C) and the solvent (D) is in the range of 40wt% to 100wt%, preferably 50wt% to 100wt%, more preferably 60wt% to 100wt%. The upper mass ratio of 100wt% means that no solvent (D) is applied, resulting in the most energy-efficient process since there is no need to separate the solvent. The lower mass ratio of 40wt% leads to an increase in the amount of the solvent (D), which must be optionally separated and possibly purified. This makes the overall process less efficient since there is no energy savings.

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

[0074] In one embodiment of the present invention, the polyoxazolidinone has an epoxy equivalent weight (EEW) of 100g / eq-5000g / eq, preferably 150g / eq-3000g / eq, more preferably 200g / eq-1500g / eq, and the epoxy equivalent weight was measured by Metrohm 888 Titrando using potentiometric hydrochloric acid titration. The epoxy sample was added to a 250mL beaker and then mixed with tetrabutylammonium bromide (TBAB) in glacial acetic acid (64.5g / L). The solution was then titrated with peracetic acid (0.1mol / L) until after the equivalence point.

[0075] The epoxy equivalent weight (EEW) of a polyoxazolidinone group-containing prepolymer is defined as the total mass of material containing one equivalent of an epoxy group.

[0076] In a first embodiment, the present invention provides a method for producing an epoxy-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); the molar ratio of the epoxy group of the polyepoxide compound (B) to the isocyanate group of the polyisocyanate compound (A) is from 2.6:1 to 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), Yb(II), Cu(II), V(II), Mo(II), Mn(II), Fe(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), Yb(I II), 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), (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 containing 1 to 10 carbon atoms and / or heteroatom-containing substituents and / or heteroatoms; Y is a halide, carbonate, nitrate, sulfate or phosphate anion, more preferably a halide or carbonate anion; n is an integer of 1, 2 or 3, At least one compound selected from the group consisting of The copolymerization is carried out at 1 bar (absolute) in the absence of an additional solvent (D-1) having a boiling point above 170°C, preferably above 165°C, more preferably above 160°C, most preferably above 150°C.

[0077] In a second embodiment, the present invention relates to a process according to the first embodiment, wherein the copolymerization is carried out in the absence of an additional solvent (D).

[0078] In a third embodiment, the present invention relates to the process according to the first or second embodiment, wherein the molar ratio of epoxy groups of the polyepoxide compound (B) to isocyanate groups of the polyisocyanate compound (A) 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.

[0079] In a fourth embodiment, the present invention relates to a method according to any one of the first to third embodiments, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1) and / or an aromatic polyisocyanate compound (A-2), preferably an aromatic polyisocyanate compound (A-2).

[0080] In a fifth embodiment, the present invention relates to a process according to any of the first to fourth embodiments, 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).

[0081] In a sixth embodiment, the present invention relates to a method according to any one of the first to fifth 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).

[0082] In a seventh embodiment, the present invention relates to a method according to any of the first to fifth 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).

[0083] In an eighth embodiment, the present invention relates to a method according to any of the first to fifth 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).

[0084] In a ninth embodiment, the present invention relates to a method according to any of the first to fifth 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).

[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 at least one compound selected from the group consisting of LiCl, LiBr, LiI, MgCl2, MgBr2, MgI2, SmI3, Ph4SbBr, Ph4SbCl, Ph4PBr, Ph4PCl, Ph3(C6H4-OCH3)PBr, Ph3(C6H4-OCH3)PCl, Ph3(C6H4F)PCl and Ph3(C6H4F)PBr, preferably LiCl, LiBr and LiI, most preferably LiCl.

[0086] In an eleventh embodiment, the present invention relates to a process according to any of the first to tenth 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).

[0087] In a twelfth embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: i) mixing a polyisocyanate compound (A), a polyepoxide compound (B), and a catalyst (C) to form a mixture (i); ii) copolymerizing mixture (i); The present invention relates to a method according to any one of the first to eleventh embodiments, including the above-mentioned.

[0088] In a thirteenth embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: α) mixing at least a portion of the polyepoxide compound (B) and the catalyst (C) to form a mixture (α); β) adding a polyisocyanate compound (A) to the mixture (α) under copolymerization conditions; The present invention relates to a method according to any one of the first to eleventh embodiments, including the above-mentioned.

[0089] In a fourteenth embodiment, the present invention relates to an epoxy-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 epoxy terminated polyoxazolidinone according to the fourteenth embodiment, having an epoxy equivalent weight (EEW) of 100g / eq-5000g / eq, preferably 150g / eq-3000g / eq, wherein the epoxy equivalent weight is measured by Metrohm 888 Titrando using potentiometric hydrochloric acid titration, the epoxy sample is added to a 250mL beaker, then mixed with tetrabutylammonium bromide (TBAB) in glacial acetic acid (64.5g / L), and then the solution is titrated with peracetic acid (0.1mol / L) until after the equivalence point.

[0091] In a sixteenth embodiment, the present invention provides a method for manufacturing a semiconductor device comprising: γ) mixing at least a portion of the polyisocyanate compound (A) and the catalyst (C) to form a mixture (γ); δ) adding a polyepoxide compound (B) to the mixture (γ) under copolymerization conditions; The present invention relates to a method according to any one of the first to eleventh embodiments, including the above-mentioned. [Brief description of the drawings]

[0092] [Figure 1] As can be seen in Figure 1, a signal characteristic of an oxazolidinone carbonyl group was observed at 1749 cm-1 in the IR spectrum. As can be seen in Figure 1, no signal characteristic of an isocyanurate group was observed in the IR spectrum. [Diagram 2] As can be seen in Figure 2, in the IR spectrum, a characteristic signal of the oxazolidinone carbonyl group was observed at 1749 cm-1 along with many other peaks indicative of by-products. As can be seen in Figure 2, in the IR spectrum, a characteristic signal of the oxazolidinone carbonyl group was observed at 1749 cm-1, while the signal at 1725 cm-1 can be assigned to the urethane carbonyl moiety and the signal at 1705 cm-1 to the carbonyl group of the isocyanurate formed. [Diagram 3] As can be seen in FIG. 3, in the IR spectrum, a characteristic signal of the oxazolidinone carbonyl group is observed at 1749 cm-1, while the signal at 1725 cm-1 can be assigned to the urethane carbonyl moiety and the signal at 1705 cm-1 to the carbonyl group of the formed isocyanurate. [Figure 4] As can be seen in FIG. 4, in the IR spectrum, a characteristic signal of the oxazolidinone carbonyl group is observed at 1749 cm-1, while the signal at 1725 cm-1 can be assigned to the urethane carbonyl moiety and the signal at 1705 cm-1 to the carbonyl group of the isocyanurate formed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLES

[0093] The present invention will now be further described with reference to the following examples, without however wishing to be limited to these examples.

[0094] Diisocyanate compound (A) MDI: Methylene diphenyl diisocyanate (MDI 1806), >99%, Covestro AG (Germany).

[0095] Epoxide Compounds (B) BI: Araldite DY-D / CH butanediol diglycidyl ether (BDDE), EEW 118g / eq-125g / eq, was obtained from HUNTSMAN Advanced Materials (Deutschland) GmbH (Germany). Because Araldite DY-D / CH produces a significant amount of compounds that are not ideal structures (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 x functionality) = 202.25 / 121 x 2 = 0.835

[0096] B-II: Araldite DY 026 butanediol diglycidyl ether (BDDE), EEW 110 g / eq–115 g / eq (higher purity) was obtained from HUNTSMAN Advanced Materials (Deutschland) GmbH (Germany). Since Araldite DY 026 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 x functionality) = 202.25 / 112.5 x 2 = 0.899

[0097] Catalyst (C) LiCl Lithium chloride, >99% purity, was obtained from Sigma Aldrich (Germany). DMC A double metal cyanide (DMC) catalyst prepared according to Example 6 of WO 2001 / 80994. Ph4PBr Tetraphenylphosphonium bromide, 97%, was obtained from Sigma Aldrich (Germany).

[0098] Solvent (D) o-DCB Ortho-dichlorobenzene, 99% purity, anhydrous, was obtained from Sigma-Aldrich (Germany). Sul sulfolane, purity ≥99%, anhydrous, was obtained from Sigma-Aldrich (Germany).

[0099] MDI, LiCl, and BDDE were used as received without further purification. Sulfolane was used after melting at 50° C. and drying over molecular sieves. o-DCB was dried over molecular sieves before use.

[0100] Addition Protocol Batch Protocol: All ingredients are weighed into a glass flask which is placed in a preheated oil bath at 175° C. and stirred immediately. Semi-batch protocol: Catalyst (C) and diepoxide (B) are prepared in a glass flask and heated to 175° C. The diisocyanate compound is added to the reactor containing catalyst (C) dissolved in the diepoxide compound while continuously stirring the mixture.

[0101] 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 the polyoxazolidinone prepolymer was then applied to the diamond probe and measured with 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 0.1 μm to 0.5 μm.

[0102] Epoxy equivalent weight (EEW) Epoxy equivalent weight was measured by Metrohm 888 Titrando using potentiometric hydrochloric acid titration. Epoxy samples were added to a 250 mL beaker and then mixed with tetrabutylammonium bromide (TBAB) in glacial acetic acid (64.5 g / L). The solution was then titrated with peracetic acid (0.1 mol / L) until the equivalence point.

[0103] GPC GPC measurements were performed at 40 °C in tetrahydrofuran (THF, flow rate of 1.0 mL / min). The column set consisted of three consecutive columns (PSS SDV, 5 μm, 8 × 50 mm precolumn, two PSS SDV linear S, 5 μm, 8 × 300 mm). Samples (concentration 2 g / L-3 g / L, injection volume 20 μL) were injected using an Agilent technologies 1200 series autosampler. Concentrations were observed at the column outlet using an Agilent 1200 series RID detector. Raw data were processed using the WinGPC Unity software package from PSS. To calculate the molecular weight distribution, polystyrenes of known molecular weight were used as references (PSS ReadyCal kits were used in the range of 266 Da-66000 Da). Number average molecular weights measured by GPC are reported in the examples as M n (GPC).

[0104] Color index according to the Gardner scale: The Gardner colour index was determined using a Hach Lico 690. Thus, samples of the product mixture were filled into cuvettes which were subsequently analysed according to DIN EN ISO 1557.

[0105] Viscosity measurement: Viscosity values ​​were determined with 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. The viscosity is reported in mPa s (following the procedure according to DIN EN ISO 3219 / A.3).

[0106] Reactor The reaction was carried out in a 100 ml two-neck round-bottom flask under a continuous flow of argon. A syringe pump (KD Scientific Inc.) was connected to the flask for the addition of the diisocyanate compound to the catalyst (C) dissolved in the diepoxide compound.

[0107] Example 1: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY-D / CH as compound (BI), MDI 1806 as compound (A), and LiCl as compound (C) according to a batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.3:1. The reactor was charged with LiCl (0.059 g, 1.4 mmol), MDI 1806 (12.51 g, 50 mmol) and Araldite DY-D / CH (40.45 g, 167 mmol BDDE). The reactor was sealed and inertized with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h, the reaction mixture was cooled to room temperature.

[0108] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0109] As shown in Figure 1, the IR spectrum shows a characteristic signal of the oxazolidinone carbonyl group at 1749 cm -1 was observed.

[0110] As can be seen in FIG. 1, no characteristic signals of isocyanurate groups were observed in the IR spectrum.

[0111] The EEW was determined to be 250 g / eq.

[0112] Molecular weight analysis using GPC showed an average molecular weight of 533 g / mol and a polydispersity index of 3.42.

[0113] The color index was determined to be 8.2 on the Gardner scale.

[0114] The viscosity of the product was determined to be 6720 mPa·s.

[0115] Example 2: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY 026 as compound (B-II), MDI 1806 as compound (A), and LiCl as compound (C) according to a batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.9:1. The reactor was charged with LiCl (0.052 g, 1.23 mmol), MDI 1806 (10.3 g, 41 mmol) and Araldite DY 026 (35.6 g, 158 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h the reaction mixture was cooled to room temperature.

[0116] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0117] In the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group is at 1749 cm -1 was observed.

[0118] In the IR spectrum, no characteristic signals of isocyanurate groups were observed.

[0119] The EEW was determined to be 217 g / eq.

[0120] Molecular weight analysis using GPC showed an average molecular weight of 473 g / mol and a polydispersity index of 2.67.

[0121] The color index was determined to be 7.4 on the Gardner scale.

[0122] The viscosity of the product was determined to be 1880 mPa·s.

[0123] Example 3: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY / D-CH as compound (BI), MDI 1806 as compound (A), and LiCl as compound (C) according to a semi-batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.3:1. The reactor was charged with LiCl (0.03 g, 0.7 mmol) and Araldite DY / D-CH (20.23 g, 84 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, MDI 1806 (6.25 g, 25 mmol) as compound (A) was added at a rate of 1 mL / min. After 3.5 h, the reaction mixture was cooled to room temperature.

[0124] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0125] In the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group is at 1749 cm -1 was observed.

[0126] In the IR spectrum, no characteristic signals of isocyanurate groups were observed.

[0127] The EEW was determined to be 247 g / eq.

[0128] Molecular weight analysis using GPC showed an average molecular weight of 416 g / mol and a polydispersity index of 3.37.

[0129] The color index was determined to be 9.1 on the Gardner scale.

[0130] The viscosity of the product was determined to be 4790 mPa·s.

[0131] Example 4: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY-D / CH as compound (BI), MDI 1806 as compound (A) and LiCl as compound (C) according to a batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.3:1 in the presence of a mixture of ortho-dichlorobenzene and sulfolane as compound (D). The aforementioned reactor was charged with LiCl (0.045 g, 1.05 mmol), MDI 1806 (9.38 g, 37.5 mmol), Araldite DY-D / CH (30.34 g, 125 mmol BDDE), ortho-dichlorobenzene (8.3 mL), and sulfolane (2.5 mL). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h, the reaction mixture was cooled to room temperature.

[0132] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0133] In the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group is at 1749 cm -1 was observed.

[0134] In the IR spectrum, no characteristic signals of isocyanurate groups were observed.

[0135] The EEW was determined to be 322 g / eq.

[0136] To remove the solvent, the mixture was heated to 200° C., above the boiling point of o-DCB, for 5 hours. During this process, the sample became highly viscous and exhibited an increase in color.

[0137] Molecular weight analysis using GPC showed an average molecular weight of 508 g / mol and a polydispersity index of 3.23 before distillation and an average molecular weight of 638 g / mol and a polydispersity index of 6.0 after distillation.

[0138] The colour index was determined to be 8.0 on the Gardner scale before distillation and 8.4 on the Gardner scale after distillation.

[0139] The viscosity of the product was determined to be 569 mPa·s before distillation and 74200 mPa·s after distillation.

[0140] Example 5 (Comparative): Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY / D-CH as compound (BI), MDI 1806 as compound (A) and LiCl as compound (C) according to the batch protocol with a molar ratio of epoxy groups to isocyanate groups of 2.5:1. The reactor was charged with LiCl (0.052 g, 1.23 mmol), MDI 1806 (14.7 g, 58.7 mmol) and Araldite DY-D / CH (35.6 g, 147 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h the reaction mixture was cooled to room temperature.

[0141] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0142] In the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group is at 1749 cm -1 was observed.

[0143] In the IR spectrum, no characteristic signals of isocyanurate groups were observed.

[0144] The EEW was determined to be 323 g / eq.

[0145] Molecular weight analysis using GPC showed an average molecular weight of 581 g / mol and a polydispersity index of 3.78.

[0146] The color index was determined to be 10.4 on the Gardner scale.

[0147] The viscosity of the product was determined to be 68600 mPa·s.

[0148] Example 6: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY / D-CH as compound (BI), MDI 1806 as compound (A) and LiCl as compound (C) according to the batch protocol with a molar ratio of epoxy groups to isocyanate groups of 1.7:1. The reactor was charged with LiCl (0.052 g, 1.23 mmol), MDI 1806 (22.0 g, 88 mmol) and Araldite DY-D / CH (35.6 g, 147 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min, the reaction was stopped due to solidification of the reaction mixture.

[0149] As can be seen in Figure 2, in the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group appears at 1749 cm along with many other peaks indicative of by-products. -1 was observed.

[0150] As shown in Figure 2, the IR spectrum shows a characteristic signal of the oxazolidinone carbonyl group at 1749 cm -1 On the other hand, at 1725 cm -1 The signal at 1705cm corresponds to the urethane carbonyl moiety. -1 The signal at can be assigned to the carbonyl group of the isocyanurate formed.

[0151] Determination of the EEW was not possible.

[0152] Analysis of the molecular weight using GPC was not possible.

[0153] The color index was determined to be greater than 18 and therefore outside the range of the Gardner scale.

[0154] Example 7 (Comparative): Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY-D / CH as compound (BI), MDI 1806 as compound (A) and DMC as compound (C) according to the batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.3:1. The reactor was charged with DMC (0.0018 g), MDI 1806 (12.51 g, 50 mmol) and Araldite DY-D / CH (40.45 g, 167 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h the reaction mixture was cooled to room temperature.

[0155] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0156] As shown in Figure 3, the characteristic signal of the oxazolidinone carbonyl group in the IR spectrum is at 1749 cm -1 On the other hand, at 1725 cm -1 The signal at 1705cm corresponds to the urethane carbonyl moiety. -1 The signal at can be assigned to the carbonyl group of the isocyanurate formed.

[0157] The EEW was determined to be 233 g / eq.

[0158] Molecular weight analysis using GPC showed an average molecular weight of 396 g / mol and a polydispersity index of 3.86.

[0159] The color index was determined to be 9.0 on the Gardner scale.

[0160] The viscosity of the product was determined to be 3260 mPa·s.

[0161] Example 8 (Comparative): Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY-D / CH as compound (BI), MDI 1806 as compound (A) and DMC as compound (C) following a batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.3:1 (similar to Example 7 but with increased catalyst concentration). The reactor was charged with DMC (0.059 g), MDI 1806 (12.51 g, 50 mmol) and Araldite DY-D / CH (40.45 g, 167 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h, the reaction mixture was cooled to room temperature.

[0162] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0163] As shown in Figure 4, the characteristic signal of the oxazolidinone carbonyl group in the IR spectrum is at 1749 cm -1 On the other hand, at 1725 cm -1 The signal at 1705cm corresponds to the urethane carbonyl moiety. -1 The signal at can be assigned to the carbonyl group of the isocyanurate formed.

[0164] The EEW was determined to be 233 g / eq.

[0165] Molecular weight analysis using GPC showed an average molecular weight of 483 g / mol and a polydispersity index of 6.62.

[0166] The color index could not be determined because the product samples were inhomogeneous and turbid.

[0167] The viscosity of the product could not be determined because the product sample was too inhomogeneous.

[0168] Example 9: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY-D / CH as compound (BI), MDI 1806 as compound (A), and tetraphenylphosphonium bromide as compound (C) according to a batch protocol with a molar ratio of epoxy groups to isocyanate groups of 3.3:1. The reactor was charged with Ph4PBr (1.2 g, 2.43 mmol), MDI 1806 (15.55 g, 124 mmol) and Araldite DY-D / CH (50 g, 410 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h the reaction mixture was cooled to room temperature.

[0169] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0170] In the IR spectrum, the characteristic signal of the oxazolidinone carbonyl group is at 1749 cm -1 was observed.

[0171] The EEW was determined to be 227 g / eq.

[0172] Molecular weight analysis using GPC showed an average molecular weight of 394 g / mol and a polydispersity index of 3.29.

[0173] The color index was determined to be 9.0 on the Gardner scale.

[0174] The viscosity of the product was determined to be 4030 mPa·s.

[0175] Example 10: Synthesis of epoxy-terminated polyoxazolidinone-based prepolymer using Araldite DY-D / CH as compound (BI), MDI 1806 as compound (A), and tetraphenylphosphonium bromide as compound (C) according to a batch protocol with a molar ratio of epoxy groups to isocyanate groups of 2.5:1. The reactor was charged with Ph4PBr (1.2 g, 2.43 mmol), MDI 1806 (20.53 g, 164 mmol) and Araldite DY-D / CH (50 g, 410 mmol BDDE). The reactor was sealed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 h the reaction mixture was cooled to room temperature.

[0176] The isocyanate band (2260 cm) in the IR spectrum of the reaction mixture -1 The absence of ) indicated completion of the reaction.

[0177] In the IR spectrum, 1725 cm -1 At the same time, a signal characteristic of the oxazolidinone carbonyl group was observed at 1749 cm -1 was observed.

[0178] The EEW was determined to be 370 g / eq.

[0179] Molecular weight analysis using GPC showed an average molecular weight of 662 g / mol and a polydispersity index of 4.55.

[0180] The color index was determined to be 9.0 on the Gardner scale.

[0181] The viscosity of the product was determined to be 33000 mPa·s.

[0182] [Table 1]

Claims

1. A method for producing an epoxy-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) and, optionally, a solvent (D-1) having a boiling point above 170° C. at 1 bar (absolute), the molar ratio of the epoxy groups of the polyepoxide compound (B) to the isocyanate groups of the polyisocyanate compound (A) is 2.8:1 to less than 5:1; The catalyst (C) LiCl, LiBr, LiI, MgCl 2 , MgBr 2 , MgI 2 , SmI 3 , 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 (C6H4F)PCl and Ph3(C6H4F)PBr, At least one compound selected from the group consisting of The catalyst (C) is used in a molar amount of 0.001 mol % to 2.0 mol % based on the polyepoxide compound (B); The copolymerization is carried out at 1 bar (absolute) under conditions where, when using said solvent (D-1), the solvent is less than 5% by weight based on the total weight of the starting materials for the copolymerization, The method, wherein the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

2. The process according to claim 1, wherein the copolymerization is carried out in the absence of the solvent (D-1) and other solvents.

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

4. The method according to any one of claims 1 to 2, wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1).

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

6. The catalyst (C) is LiCl, LiBr, LiI, Ph ４ PBr and Ph ４ The method according to any one of claims 1 to 5, wherein the compound is at least one compound selected from the group consisting of PCl.

7. i) mixing the polyisocyanate compound (A), the polyepoxide compound (B), and the catalyst (C) to form a mixture (i); ii) copolymerizing said mixture (i); The method according to any one of claims 1 to 6, comprising:

8. α) mixing at least a portion of the polyepoxide compound (B) and the catalyst (C) to form a mixture (α); β) adding the polyisocyanate compound (A) to the mixture (α) under copolymerization conditions; The method according to any one of claims 1 to 6, comprising:

9. Epoxy-terminated polyoxazolidinone obtainable by the method according to any one of claims 1 to 8.

10. 10. The epoxy terminated polyoxazolidinone of claim 9 having an epoxy equivalent weight (EEW) of 100 g / eq to 5000 g / eq, and the epoxy equivalent weight is measured by a Metrohm 888 Titrando using potentiometric hydrochloric acid titration by adding an epoxy sample to a 250 mL beaker, mixing with 64.5 g / L of tetrabutylammonium bromide in glacial acetic acid, and then titrating the solution with 0.1 mol / L peracetic acid past the equivalence point.

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