Method for preparing epoxy group-terminated polyoxazolidinone

Abstract

The present invention relates to a method for preparing epoxy-terminated polyoxazolidinones, comprising 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 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 wherein the copolymerization is carried out 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 at 1 bar (absolute pressure). The present invention also relates to the resulting epoxy-terminated polyoxazolidinones.

Description

[0001] The present invention relates to a method for preparing epoxy-terminated polyoxazolidinones, comprising 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 epoxy groups of the polyepoxide compound (B) to isocyanate groups of the polyisocyanate compound (A) is from 2.6:1 to less than 25:1, and wherein the copolymerization is carried out 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 at 1 bar (absolute pressure). The present invention also relates to the resulting epoxy-terminated polyoxazolidinones.

[0002] Oxazolidinone is that the cycloaddition of widely used structural unit and epoxide and isocyanate seems to be the one-pot synthetic route of its convenience for preparation in pharmaceutical applications. Expensive catalyst, reactive polar solvent, long reaction time and low chemical selectivity are common (ME Dyen and D. Swern, Chem. Rev., 67, 197, 1967) in the early reports about the synthesis of oxazolidinone. Due to these shortcomings, need to be used for the preparation of the alternative method of oxazolidinone, especially for the application of oxazolidinone as the structural unit in polymer application.

[0003] Scientific publication J.Polym.Sci.8 (1970) 2759-2773 discloses polyoxazolidinone prepared in the presence of alkali metal halide catalyst by various diepoxides and various diisocyanates.Under reflux condition, the solution of diepoxides of equimolar amount and diisocyanates was dropwise added in the reactor containing the LiCl catalyst dissolved in the DMF in 1 hour, and then under reflux condition, after-reaction of 12 to 23 hours was carried out so that this reaction was complete.

[0004] EP 0 113 575 A1 discloses a powder coating composition comprising an epoxy-terminated polyoxazolidone, which is prepared by reacting a diepoxide with a diisocyanate, wherein the ratio of the epoxide equivalent to the isocyanate equivalent is 10:1 to 1.1:1. The resulting polyoxazolidone has an epoxide equivalent weight of 250 to 4000. In Example 1, an epoxy-terminated polyoxazolidone powder is prepared, wherein in a first step, a carbamate is formed by reacting toluene diisocyanate with a stoichiometric excess of ethanol in the presence of dibutyltin dilaurate, and then the carbamate is reacted with the epoxide in the presence of triethyldiamine to form an oxazolidone. In Examples 2 and 3, epoxy-terminated polyoxazolidone powders are synthesized in the presence of tetraethylammonium bromide catalyst with an epoxide equivalent ratio of 1.6 and 1.96 to isocyanate equivalent.

[0005] US 2002 / 0037975 A1 describes epoxy resins containing oxazolidone rings, wherein the epoxy resins are prepared by first obtaining a blocked polyurethane diisocyanate via reaction of a diisocyanate with an alcohol and reacting it with a diepoxide, wherein the reaction can be carried out in the presence of a tertiary amine catalyst and optionally a tin promoter.

[0006] DE 37 20 759 A1 provides a process for preparing oligomeric oxazolidinone-containing polyepoxides based on diepoxides and diisocyanates in the presence of phosphonium carboxylates or phosphonium halides as catalyst systems. In the disclosed embodiments, the ratio of NCO groups of the diisocyanate used to the epoxy groups of the diepoxide used is 1:1.6 to 1:2.0, and solid polyoxazolidinones with epoxy equivalent weights of 460 to 711 are obtained.

[0007] In Pelzer et al. (European Polymer Journal 107 (2018)), the formation of oxazolidinones was studied by the reaction of 4,4-methylenediphenyl diisocyanate (MDI) with o-cresol glycidyl ether (OGCE) or bisphenol A diglycidyl ether (BADGE) in the presence of various tetra-n-butylammonium halides, using molar ratios of BADGE to MDI up to 3 to 1. However, significant amounts of by-products, namely isocyanurates, were detected.

[0008] WO 2019 / 081210 A1 discloses a method for preparing an oxazolidinone compound, wherein an isocyanate composition comprising at least one isocyanate compound is reacted with an epoxide composition comprising an epoxide compound, wherein a multimetal cyanide compound is used as a catalyst, wherein the catalyst is used at a low catalyst concentration of 28 ppm to 34 ppm. The obtained oxazolidinone compound has a carbonyl content of 1.750 g / cm2. -1 The characteristic signal of the oxazolidinone carbonyl group can be detected at about 1725 cm -1 The signal at , which is assigned to the carbamate carbonyl moiety as a by-product.

[0009] Therefore, the object of the present invention is to determine the simple one-step method for preparing the polyoxazolidinone of epoxy group end-capping, the polyoxazolidinone of epoxy group end-capping has the epoxide equivalent weight of limitation and preferably combines the viscosity of low polydispersity and reduction so that be used for further polymerization application.In this respect, side reaction (for example the formation of isocyanurate or polyurethane) should be reduced or avoided.In addition, the use of the commonly used high boiling point solvent (it needs to be removed at high temperature) in the synthesis of oxazolidinone should be avoided to reduce the quantity of by-products, obtain less painted oxazolidinone, and obtain more energy-efficient method.

[0010] Surprisingly, it has been found that this problem can be solved by a process for preparing epoxy group-terminated polyoxazolidinones comprising the steps of: 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 catalyst (C);

[0011] 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;

[0012] The catalyst (C) is at least one compound selected from the following:

[0013] Li(I), Rb(I), Cs(I), Ag(I), Au(I),

[0014] 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),

[0015] Sc(III), Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III),

[0016] Er(III), Tm(III), Yb(III), Lu(III), Hf(III), Nb(III), Ta(III), Cr(III), Ru(III), Os(III), Rh(III), Ir(III),

[0017] Al(III), Ga(III), In(III), Tl(III), Ge(III),

[0018] Ce(IV), Ti(IV), Zr(IV), Hf(IV), Nb(IV), Mo(IV), W(IV), Ir(IV), Pt(IV), Sn(IV), Pb(IV),

[0019] Nb(V), Ta(V), Bi(V),

[0020] Mo(VI), W(VI) and

[0021] Compound represented by formula (I)

[0022] [M(R1)(R2)(R3)(R4)]+n Yn- (I)

[0023] Wherein M is phosphorus or antimony, preferably phosphorus;

[0024] wherein (R1), (R2), (R3), (R4) are independently selected from a linear or branched alkyl group containing 1 to 22 carbon atoms which is optionally substituted by heteroatoms and / or substituents containing heteroatoms, an alicyclic group containing 3 to 22 carbon atoms which is optionally substituted by heteroatoms and / or substituents containing heteroatoms, a C1 to C3 alkyl-bridged alicyclic group containing 3 to 22 carbon atoms which is optionally substituted by heteroatoms and / or substituents containing heteroatoms, and an aryl group containing 6 to 18 carbon atoms which is optionally substituted by one or more alkyl groups containing 1 to 10 carbon atoms and / or substituents containing heteroatoms and / or heteroatoms,

[0025] wherein Y is a halide, carbonate, nitrate, sulfate or phosphate anion, more preferably a halide or carbonate, and

[0026] wherein n is an integer of 1, 2 or 3;

[0027] And wherein the copolymerization is carried out 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 at 1 bar (absolute pressure).

[0028] The term "polyoxazolidone" as used herein is intended to mean a compound containing at least two oxazolidone groups in the molecule. The term "epoxy-terminated" polyoxazolidone relates to a polyoxazolidone compound in which the molar ratio of the epoxy groups of the polyepoxide compound (B) to the isocyanate groups of the polyisocyanate compound (A) is 2.6:1 or more, so that there is no terminal isocyanate group in the polyoxazolidone compound according to the present invention.

[0029] In one embodiment of the process 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 is generally very slow. At temperatures above 280° C., the amount of undesirable secondary products increases significantly.

[0030] As used herein, the term "polyisocyanate compound" is intended to mean a compound having two or more isocyanate groups.

[0031] 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).

[0032] In one embodiment of the process according to the invention, the polyisocyanate compound (A) is at least one polyisocyanate obtainable in various ways, for example by phosgenation in the liquid or gas phase, or by a phosgene-free route, for example by thermal carbamate cleavage.

[0033] 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: g / mol of polyisocyanates with aliphatically, cycloaliphatically, araliphatically and / or aromatically bonded isocyanate groups, examples being 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, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,12-diisocyanatododecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-diisocyanatocyclohexane. 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 polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetriaone structure, which is prepared by modification of simple aliphatic and / or alicyclic diisocyanates (e.g. those of the abovementioned type), for example as described in J. Prakt. Chem. 336 (1994) 185 - 200, described in DE-A 1 670666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700209, DE-A 3 900 053 and DE-A 3 928 503, or described in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299, or by a mixture of at least two such polyisocyanates, and 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatoprop-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)-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, isomers of diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, diisododecylphenylene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxyphenylene diisocyanate Benzene-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diisocyanato diphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanato diphenylethane, 1,5-diisocyanato naphthalene (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'-pentaisocyanate, and polynuclear homologues of diisocyanatodiphenylmethane known as "polymer-MDI", and monomers which may be prepared from 2,4- and / or 2,Polyisocyanates having a urethane and / or isocyanurate structure obtained by reaction and / or oligomerization (preferably trimerization) of 6-TDI with polyols, which can be obtained by any known process, for example as described in DE-A 870 400, DE-A 953 012, DE-A 1 090196, EP-A 0 546 399, CN 105218780, CN 103881050, CN 101717571, U.S. Pat. No. 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915 or JP 56059828, or mixtures of at least two such polyisocyanates, and those polyisocyanate compounds with aromatic and aliphatic isocyanate groups, for example the mixed trimers or allophanates of 2,4- and / or 2,6-TDI with HDI described in DE-A 1 670 667, EP-A 0 078 991, EP-A 0 696 606 and EP-A 0 807 623.

[0034] More preferably, 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 being 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(isocyanato)cyclohexane. The invention relates to polyisocyanates of the type described herein, for example 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 any polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetriaone structure, which are prepared by modification of simple aliphatic and / or cycloaliphatic diisocyanates, for example those of the abovementioned type, as described, for example, in J. Prakt. Chem. 336 (1994) 185 - 200, 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 described in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299, as well as 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropyl-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)- 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-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, 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 isomers naphthalene triisocyanate and methylnaphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene and the polynuclear homologues of diisocyanatodiphenylmethane known as “polymer-MDI”, and polyisocyanates having a urethane and / or isocyanurate structure obtainable from the monomeric 2,4- and / or 2,6-TDI by reaction and / or oligomerization (preferably trimerization) with polyols, which can be obtained by any known process, for example as described in DE-A 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546 399, CN105218780, CN 103881050, CN 101717571, U.S. Pat. No. 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915 or JP 56059828, as well as those polyisocyanate compounds with aromatic and aliphatic isocyanate groups, 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, the mixed trimers or allophanates of 2,4- and / or 2,6-TDI with HDI.

[0035] And most preferably, the polyisocyanate compound (A) 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), and 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatopropyl-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).

[0036] It is also possible to use a mixture of two or more of the aforementioned polyisocyanate compounds (A).

[0037] As used herein, the term "aromatic polyisocyanate compound" is intended to mean a compound having two or more isocyanate groups and an aromatic moiety.

[0038] 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).

[0039] In a preferred embodiment of the process according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound and is selected from araliphatic and / or aromatic diisocyanates and triisocyanates having a molecular weight range of 160 g / mol to 600 g / mol, for example 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatoprop-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-diisocyanate, 1,3-bis(isocyanatomethyl)-4-ethylbenzene. 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-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) ester, 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 diisocyanate 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, and polynuclear homologues of diisocyanatodiphenylmethane known as "polymer-MDI", as well as monomers which can be prepared from 2,4- and / or 2,Polyisocyanates having a urethane and / or isocyanurate structure obtained by reaction and / or oligomerization (preferably trimerization) of 6-TDI with polyols, which can be obtained by any known process, for example as described in DE-A 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546 399, CN 105218780, CN 103881050, CN 101717571, US 3183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A 2174 967, JP 63260915 or JP 56059828, as well as those polyisocyanate compounds with aromatic and aliphatic isocyanate groups, for example the mixed trimers or allophanates of 2,4- and / or 2,6-TDI with HDI described in DE-A 1 670 667, EP-A 0 078 991, EP-A 0 696 606 and EP-A 0 807 623.

[0040] In a more preferred embodiment of the process according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound and is selected from araliphatic and / or aromatic diisocyanates and triisocyanates having a molecular weight range of 160 g / mol to 600 g / mol, for example 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatoprop-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)- 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, isomers of diethylphenylene diisocyanate, 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 triisocyanate and methylnaphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'-pentaisocyanate, and polynuclear homologues of diisocyanatodiphenylmethane, known as "polymer-MDI", and polyisocyanates having a urethane and / or isocyanurate structure obtainable from monomeric 2,4- and / or 2,6-TDI by reaction with polyols and / or oligomerization, preferably trimerization, which can be obtained by any known process, for example as described in DE-A 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546 399, CN 105218780, CN 103881050, CN 101717571, U.S. Pat. No. 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A2 174 967, JP 63260915 or JP 56059828, or mixtures of at least two such polyisocyanates, and those polyisocyanate compounds with aromatic and aliphatic isocyanate groups, for example the mixed trimers or allophanates of 2,4- and / or 2,6-TDI with HDI described in DE-A 1 670 667, EP-A 0 078 991, EP-A 0 696 606 and EP-A 0 807 623.

[0041] In a most preferred embodiment of the process according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound and is selected from 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanatoprop-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).

[0042] It is also possible to use a mixture of two or more aromatic polyisocyanate compounds (A-2).

[0043] As used herein, the term "aliphatic polyisocyanate compound" is intended to mean a compound having two or more isocyanate groups and having no aromatic moiety.

[0044] In a less preferred embodiment of the process according to the invention, the polyisocyanate compound (A) is an aliphatic or cycloaliphatic polyisocyanate (A-1).

[0045] 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: aliphatic polyisocyanate having a molecular weight ranging from 140 g / mol to 400 g / mol; g / mol of polyisocyanates with aliphatically or cycloaliphatically bonded isocyanate groups, examples being 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, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,12-diisocyanatododecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanato)cyclohexane. methyl)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 polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetriaone structure, which is prepared by modification of simple aliphatic and / or cycloaliphatic diisocyanates, for example those of the abovementioned type, as described, for example, in J. Prakt. Chem. 336 (1994) 185 – 200, 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 in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299, or by mixtures of at least two such polyisocyanates.

[0046] More preferably, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from the group consisting of polyisocyanates having aliphatic, cycloaliphatic, araliphatic and / or aromatic bonded isocyanate groups having a molecular weight in the range of 140 g / mol to 400 g / mol, examples being 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(isocyanato)cyclohexane. The invention relates to polyisocyanates of the type described herein, for example 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 any polyisocyanate having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetriaone structure, which are prepared by modification of simple aliphatic and / or cycloaliphatic diisocyanates, for example those of the abovementioned type, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200, 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 in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299, or by mixtures of at least two such polyisocyanates.

[0047] And most preferably, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from the following: 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).

[0048] It is also possible to use a mixture of two or more of the aforementioned polyisocyanate compounds (A-1).

[0049] As used herein, the term "polyepoxide compound" is intended to mean a compound having two or more epoxy groups.

[0050] 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).

[0051] In a preferred embodiment of the present invention, the epoxide compound (B) is at least one compound 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)fluorine, tetrabromobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, tetramethylbisphenol A diglycidyl ether. , tetramethyl bisphenol F diglycidyl ether, tetramethyl bisphenol S diglycidyl ether, terephthalic acid diglycidyl ether, phthalic acid diglycidyl ether, trimellitic acid triglycidyl ether, 1,4-cyclohexanedicarboxylic acid diglycidyl ether, 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 (polyglycerol polyglycidyl ether), polyglycidyl ether of ethoxylated trimethylolpropane, polytetrahydrofurandiol diglycidyl ether, pentaeritrol polyglycidyl ether, vinyl cyclohexene diepoxide, limonene diepoxide, diepoxides of diunsaturated fatty acid C1-C18 alkyl esters, polyepoxides of diunsaturated ethoxylated fatty alcohols, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4'-(3,3,5-trimethylcyclohexyliden)bisphenyl diglycidyl ether ether) and isophthalic acid diglycidyl ether, tetrabromobisphenol A diglycidyl ether, cardanol-based diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxybenzene 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 species of the foregoing components.

[0052] Aliphatic di- or polyglycidyl ethers derived via epoxidation of di- or polyfunctional alcohols having an aliphatic straight-chain, aliphatic branched or alicyclic moiety consisting of 2 to 40 carbon atoms, for example ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, isosorbide diglycidyl ether, octanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyethylene triglycidyl ether, 2-ethylhexyl diglycidyl ether.

[0053] More preferably, the polyepoxide compound (B) is selected from neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1,4-cyclohexanedicarboxylic acid diglycidyl ether, 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, polytetrahydrofuran diol diglycidyl ether, pentaerythritol polyglycidyl ether, vinyl cyclohexene diepoxide, diepoxide of diunsaturated fatty acid C1-C18 alkyl ester , polyepoxides of diunsaturated ethoxylated fatty alcohols, aliphatic di- or poly(di)glycidyl ethers derived via epoxidation of di- or polyfunctional alcohols having aliphatic straight-chain, aliphatic branched or alicyclic moieties consisting of 2 to 40 carbon atoms, for example ethylene glycol diglycidyl ether, propylene glycol 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.

[0054] Most preferably, the polyepoxide compound (B) is selected from ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether.

[0055] It is also possible to use mixtures of two or more of the aforementioned polyepoxide compounds (B).

[0056] As used herein, the term "aliphatic polyepoxide compound" is intended to mean a compound having two or more epoxy groups as well as an aromatic moiety.

[0057] In a preferred embodiment of the present invention, the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0058] In a preferred embodiment of the present invention, the aliphatic polyepoxide compound (B-1) is one or more compounds and is selected from neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1,4-cyclohexanedicarboxylic acid diglycidyl ether, 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, polytetrahydrofuran diol diglycidyl ether, pentaerythritol polyglycidyl ether, vinyl cyclohexene diglycidyl ether, polyvinyl alcohol ... Epoxides, diepoxides of diunsaturated fatty acid C1-C18 alkyl esters, polyepoxides of diunsaturated ethoxylated fatty alcohols, aliphatic di- or poly(di)glycidyl ethers derived via epoxidation of di- or polyfunctional alcohols having an aliphatic straight-chain, aliphatic branched or alicyclic moiety consisting of 2 to 40 carbon atoms, for example ethylene glycol diglycidyl ether, propylene glycol 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.

[0059] In a more preferred embodiment of the present invention, the aliphatic polyepoxide compound (B-1) is one or more compounds and is selected from hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol triglycidyl ether, polyglycidyl ether of ethoxylated trimethylolpropane, polytetrahydrofuran diol diglycidyl ether, pentaerythritol polyglycidyl ether, diepoxides of diunsaturated fatty acid C1-C18 alkyl esters, aliphatic di- or poly(di)glycidyl ethers derived from epoxidation of di- or polyfunctional alcohols having aliphatic straight-chain, aliphatic branched or alicyclic moieties consisting of 2 to 40 carbon atoms, such as ethylene glycol 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.

[0060] Most preferably, the aliphatic polyepoxide compound (B-1) is one or more compounds and is selected from ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether.

[0061] It is also possible to use a mixture of two or more of the aforementioned aliphatic polyepoxide compounds (B-1).

[0062] As used herein, the term "aromatic polyepoxide compound" is intended to mean a compound having two or more epoxy groups as well as an aromatic moiety.

[0063] In an alternative preferred embodiment of the present invention, the polyepoxide compound (B) is an aromatic polyepoxide (B-2).

[0064] In a preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds and is selected from 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, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, trimellitic acid triglycidyl ether, 1,4-cyclopentadiene diglycidyl ether, 1,4-diol ... Hexanedicarboxylic acid diglycidyl ester, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4'-(3,3,5-trimethylcyclohexylidene)biphenyl diglycidyl ether, isophthalic acid diglycidyl ester, tetrabromobisphenol A, cardanol-based diglycidyl ether, 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 species of the foregoing components.

[0065] In a more preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds and is selected from 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, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, diglycidyl ether, bis-(4-hydroxyphenyl)-1,1-ethane diglycidyl ether, bis-(4-hydroxyphenyl)-1,1-isobutane diglycidyl ether, bis-(4-hydroxyphenyl) ether diglycidyl ether.

[0066] In a more preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds and is selected from 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, terephthalic acid diglycidyl ether, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, isophthalic acid diglycidyl ether, cardanol-based diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxyphenyl diglycidyl ether.

[0067] In a more preferred embodiment of the present invention, the aromatic polyepoxide compound (B-2) is one or more compounds and is selected from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, isophthalic acid diglycidyl ether. A mixture of two or more of the aforementioned aromatic polyepoxide compounds (B-2) can also be used.

[0068] 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).

[0069] 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).

[0070] 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).

[0071] 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).

[0072] Mixtures of one or more of the aforementioned aliphatic polyisocyanate compounds (A-1), aromatic polyisocyanate compounds (A-2), aliphatic polyepoxide compounds (B-1) and / or aromatic polyepoxide compounds (B-2) may also be used.

[0073] 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 is higher than 7: 1, epoxy-terminated oxazolidinone is obtained, and the ratio of oxazolidinone groups in the overall mixture is diluted by the epoxy compound (B), so that the mixture does not provide significant benefits in the final polymer compared to the use of only the epoxy compound (B) in further polymerization applications.

[0074] In a preferred embodiment of the present invention, the method comprises the following steps:

[0075] i) mixing a polyisocyanate compound (A), a polyepoxide compound (B) and a catalyst (C) to form a mixture (i);

[0076] ii) copolymerizing the mixture (i).

[0077] In an alternative preferred embodiment of the present invention, the method comprises the following steps:

[0078] α) mixing a polyepoxide compound (B) and at least a portion of a catalyst (C) to form a mixture (α);

[0079] β) Adding the polyisocyanate compound (A) to the mixture (α) under copolymerization conditions.

[0080] In a further alternative, less preferred embodiment of the invention, the method comprises the following steps:

[0081] γ) mixing a polyisocyanate compound (A) and at least a portion of a catalyst (C) to form a mixture (γ);

[0082] δ) adding the polyepoxide compound (B) to the mixture (γ) under copolymerization conditions.

[0083] The conditions of the copolymerization process at elevated temperature are explained above.

[0084] 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 2 MgBr 2 MgI 2 、SmI 3 , Ph 4 SbBr、Ph 4 SbCl、Ph 4 PBr、Ph 4 PCl、Ph 3 (C 6 H4 -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) PBr, preferably LiCl, LiBr, LiI and MgCl 2 .

[0085] In a more preferred embodiment of the present invention, the catalyst (C) is selected from LiCl, LiBr and LiI.

[0086] In a more preferred embodiment of the present invention, the catalyst (C) is LiCl.

[0087] In one embodiment of the process according to the invention, the catalyst (C) is present in a molar amount of 0.001 to 2.0 mol %, preferably in an amount of 0.01 to ≤ 1.5 mol %, more preferably ≥ 0.05 to ≤ 1.0 mol %, based on the polyepoxide compound (B).

[0088] The solvent (D), and in particular the solvent (D-1), is defined in accordance with the general definition as a substance which dissolves the solute, 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).

[0089] According to the process of the present invention, the copolymerization is carried out in the absence of an additional solvent (D-1) having a boiling point at 1 bar (absolute pressure) above 170°C, preferably above 165°C, more preferably above 160°C, and most preferably above 150°C.

[0090] The absence of the additional solvent (D-1) means that the amount of solvent (D-1) is less than 5% by weight, preferably 4% by weight, more preferably 2% by weight.

[0091] These additional solvents (D-1) are, for example, organic solvents such as linear or branched alkanes or mixtures of alkanes, mono- or polysubstituted halogenated aromatic solvents or halogenated alkane solvents, for example 1,2-dichlorobenzene, linear or cyclic esters, or polar aprotic solvents such as cyclic carbonates, for example ethylene carbonate or propylene carbonate, N -Methylpyrrolidone (NMP), sulfolane, tetramethyl urea, N , N'-dimethylethyleneurea or a mixture of the above solvents and / or other solvents. These solvents (D-1) are especially 1,2-dichlorobenzene, cyclopentane and N -N-Methylpyrrolidone (NMP).

[0092] 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 process, such as distillation, is required.

[0093] In one embodiment of the present invention, the calculated mass ratio of the sum of the diisocyanate compound (A), the diepoxide compound (B) and the catalyst (C) relative to the sum of the diisocyanate compound (A), the diepoxide compound (B), the catalyst (C) and the solvent (D) is 40% to 100% by weight, preferably 50% to 100% by weight, and more preferably 60% to 100% by weight. The upper limit mass ratio of 100% by weight means that the solvent (D) is not used, resulting in the most energy-saving method because there is no need to separate the solvent. The lower limit mass ratio of 40% by weight results in the optional inclusion of a higher amount of solvent (D), which needs to be separated and potentially purified. This results in a lower overall process efficiency due to the lack of energy saving.

[0094] A further aspect of the present invention is an epoxy-group-terminated polyoxazolidinone obtainable by the process according to the invention.

[0095] In one embodiment of the present invention, the polyoxazolidinone has an epoxy equivalent weight (EEW) of 100 g / eq to 5000 g / eq, preferably 150 g / eq to 3000 g / eq, more preferably 200 g / eq to 1500 g / eq, wherein the epoxy equivalent weight is measured using a Metrohm 888 Titrando using potentiometric hydrochloric acid titration. The epoxy sample is added to a 250 ml beaker and then mixed with tetrabutylammonium bromide (TBAB) (64.5 g / L) in glacial acetic acid. The solution is then titrated with peracetic acid (0.1 mol / L) until after the equivalent point.

[0096] The epoxy equivalent weight (EEW) of the prepolymer containing polyoxazolidone groups is defined as the total mass of the substance containing 1 equivalent of epoxy groups.

[0097] In a first embodiment, the present invention relates to a method for preparing an epoxy group-terminated polyoxazolidinone comprising 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 catalyst (C);

[0098] 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;

[0099] The catalyst (C) is at least one compound selected from the following:

[0100] Li(I), Rb(I), Cs(I), Ag(I), Au(I),

[0101] 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),

[0102] Sc(III), Y(III), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III),

[0103] Er(III), Tm(III), Yb(III), Lu(III), Hf(III), Nb(III), Ta(III), Cr(III), Ru(III), Os(III), Rh(III), Ir(III),

[0104] Al(III), Ga(III), In(III), Tl(III), Ge(III),

[0105] Ce(IV), Ti(IV), Zr(IV), Hf(IV), Nb(IV), Mo(IV), W(IV), Ir(IV), Pt(IV), Sn(IV), Pb(IV),

[0106] Nb(V), Ta(V), Bi(V),

[0107] Mo(VI), W(VI) and

[0108] Compound represented by formula (I)

[0109] [M(R1)(R2)(R3)(R4)]+n Yn- (I)

[0110] Wherein M is phosphorus or antimony, preferably phosphorus

[0111] wherein (R1), (R2), (R3), (R4) are independently selected from a linear or branched alkyl group containing 1 to 22 carbon atoms which is optionally substituted by heteroatoms and / or substituents containing heteroatoms, an alicyclic group containing 3 to 22 carbon atoms which is optionally substituted by heteroatoms and / or substituents containing heteroatoms, a C1 to C3 alkyl-bridged alicyclic group containing 3 to 22 carbon atoms which is optionally substituted by heteroatoms and / or substituents containing heteroatoms, and an aryl group containing 6 to 18 carbon atoms which is optionally substituted by one or more alkyl groups containing 1 to 10 carbon atoms and / or substituents containing heteroatoms and / or heteroatoms,

[0112] wherein Y is a halide, carbonate, nitrate, sulfate or phosphate anion, more preferably a halide or carbonate, and

[0113] wherein n is an integer of 1, 2 or 3;

[0114] And wherein the copolymerization is carried out 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 at 1 bar (absolute pressure).

[0115] In a second embodiment, the invention relates to a process according to the first embodiment, wherein the copolymerization is carried out in the absence of an additional solvent (D).

[0116] In a third embodiment, the invention relates to a method 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.

[0117] 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).

[0118] In a fifth embodiment, the present invention relates to a method according to any one 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).

[0119] 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).

[0120] In a seventh 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 aromatic polyepoxide compound (B-2).

[0121] In an eighth 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 aromatic polyisocyanate compound (A-2), and the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

[0122] In a ninth 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 aromatic polyisocyanate compound (A-2), and the polyepoxide compound (B) is an aromatic polyepoxide compound (B-2).

[0123] In a tenth embodiment, the present invention relates to a method according to any one of the first to ninth embodiments, wherein the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, LiI, MgCl 2 MgBr 2 MgI 2 、SmI 3 , Ph 4 SbBr、Ph 4 SbCl、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) PBr, preferably LiCl, LiBr and LiI, and most preferably LiCl.

[0124] In an eleventh embodiment, the invention relates to a process according to any one of the first to tenth embodiments, wherein the catalyst (C) is used in a molar amount of 0.001 to 2.0 mol %, preferably in an amount of 0.01 to ≤ 1.5 mol %, more preferably ≥ 0.05 to ≤ 1.0 mol %, based on the polyepoxide compound (B).

[0125] In a twelfth embodiment, the present invention relates to a method according to any one of the first to eleventh embodiments, comprising the steps of:

[0126] i) mixing a polyisocyanate compound (A), a polyepoxide compound (B) and a catalyst (C) to form a mixture (i);

[0127] ii) copolymerizing the mixture (i).

[0128] In a thirteenth embodiment, the present invention relates to a method according to any one of the first to eleventh embodiments, comprising the steps of:

[0129] α) mixing a polyepoxide compound (B) and at least a portion of a catalyst (C) to form a mixture (α);

[0130] β) Adding the polyisocyanate compound (A) to the mixture (α) under copolymerization conditions.

[0131] In a fourteenth embodiment, the present invention relates to an epoxy-terminated polyoxazolidinone obtainable as described in any one of the first to thirteenth embodiments.

[0132] In a fifteenth embodiment, the present invention relates to an epoxy-terminated polyoxazolidinone according to the fourteenth embodiment, having an epoxide equivalent weight (EEW) of 100 g / eq to 5000 g / eq, preferably 150 g / eq to 3000 g / eq, wherein the epoxide equivalent weight is measured using a Metrohm 888 Titrando using potentiometric hydrochloric acid titration. The epoxy sample is added to a 250 ml beaker and then mixed with tetrabutylammonium bromide (TBAB) (64.5 g / L) in glacial acetic acid. The solution is then titrated with peracetic acid (0.1 mol / L) until after the equivalent point.

[0133] In a sixteenth embodiment, the invention relates to a method according to any one of the first to eleventh embodiments, comprising the steps of:

[0134] γ) mixing a polyisocyanate compound (A) and at least a portion of a catalyst (C) to form a mixture (γ);

[0135] δ) adding the polyepoxide compound (B) to the mixture (γ) under copolymerization conditions. Example

[0136] The present invention is further described with reference to the following examples, but is not intended to be limited thereto.

[0137] Diisocyanate compound (A)

[0138] MDI: Methylene diphenyl diisocyanate (MDI 1806), >99 %, Covestro AG, Germany.

[0139] Epoxide compound (B)

[0140] BI: Araldite DY-D / CH butanediol diglycidyl ether (BDDE), EEW 118-125 g / eq; obtained from HUNTSMAN Advanced Materials (Deutschland) GmbH, Germany. Since Araldite DY-D / CH provides a significant amount of non-ideal structure compounds (BDDE), the correction factor for calculating the effective molar amount of epoxy groups was calculated based on the following formula: f :

[0141]

[0142] B-II: Araldite DY 026 butanediol diglycidyl ether (BDDE), EEW 110-115 g / eq (higher purity), obtained from HUNTSMAN Advanced Materials (Deutschland) GmbH, Germany.

[0143] Since Araldite DY 026 provides a significant amount of non-ideal structured compounds (BDDE), a correction factor for calculating the effective molar amount of epoxy groups was calculated based on the following formula f :

[0144]

[0145] Catalyst (C)

[0146] LiCl Lithium chloride, purity >99%, obtained from Sigma Aldrich, Germany.

[0147] DMC Double metal cyanide (DMC) catalyst, prepared according to Example 6 in WO 2001 / 80994 A1.

[0148] Ph 4PBr Tetraphenylphosphonium bromide, 97%, was obtained from Sigma Aldrich, Germany.

[0149] Solvent (D)

[0150] o-DCB adjacent Dichlorobenzene, 99% pure, anhydrous, was obtained from Sigma-Aldrich, Germany.

[0151] Sul Sulfolane, purity ≥99%, anhydrous, obtained from Sigma-Aldrich, Germany.

[0152] MDI, LiCl, and BDDE 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.

[0153] Add a plan

[0154] Batch Protocol: All components were weighed into a glass flask, placed in an oil bath preheated to 175 °C and stirred immediately.

[0155] Semi-batch protocol: Catalyst (C) and diepoxide (B) are provided in a glass flask and heated to 175° C. While the mixture is continuously stirred, the diisocyanate compound is added to the reactor containing the catalyst (C) dissolved in the diepoxide compound.

[0156] Characterization of polyoxazolidone prepolymer

[0157] IR

[0158] IR analysis was performed on a Bruker ALPHA-P IR spectrometer equipped with a diamond probe. The software OPUS 6.5 was used for data processing. Background spectra were recorded against ambient air. Thereafter, a small sample (2 mg) of the polyoxazolidone prepolymer was applied to the diamond probe and the spectrum was taken between 4000 and 400 cm -1 Within 4 cm -1 The IR spectrum was recorded by averaging 24 spectra obtained at a resolution of 1.5 Å.

[0159] Epoxy Equivalent Weight (EEW)

[0160] The epoxy equivalent weight was measured using a Metrohm 888 Titrando using potentiometric hydrochloric acid titration. The epoxy sample was added to a 250 ml beaker and then mixed with tetrabutylammonium bromide (TBAB) (64.5 g / L) in glacial acetic acid. The solution was then titrated with peracetic acid (0.1 mol / L) until just after the equivalent point.

[0161] GPC

[0162] The mixture was stirred at 40 °C in tetrahydrofuran (THF, flow rate: 1.0 mL min -1 ). The column set consisted of 3 consecutive columns (PSS SDV, 5 µm, 8×50 mm precolumn, 2 PSS SDV linear S, 5 µm, 8×300 mm). Samples (concentration 2–3 g L -1 , injection volume 20 µL). An Agilent 1200 series RID detector was used to track the concentration at the column outlet. The raw data were processed using the PSS WinGPC Unity software package. Polystyrene of known molecular weight was used as a reference to calculate the molecular weight distribution (using the PSS ReadyCal Kit in the region of 266 Da to 66.000 Da). The number average molecular weight measured by GPC is referred to as M in the examples. n (GPC).

[0163] Color index according to Gardner scale:

[0164] The Gardner color index is determined using a Lico 690 from Hach. For this purpose, a sample of the product mixture is placed in a cuvette and subsequently analyzed in accordance with DIN EN ISO 1557.

[0165] Viscosity measurement:

[0166] The viscosity values ​​are determined by means of a cone / plate rheometer from Anton Paar MCR 302. A shear rate ramp from 10 to 600 1 / min is used to determine the viscosity of the product. According to the procedure in accordance with DIN EN ISO 3219 / A.3, the viscosity is given in mPa·s.

[0167] Reactor

[0168] The reaction was carried out in a 100 ml two-necked round bottom flask under a continuous flow of argon. A syringe pump (KD Scientific Inc.) was connected to the flask to add the diisocyanate compound to the catalyst (C) dissolved in the diepoxide compound.

[0169] Example 1: According to the batch method, the molar ratio of epoxy groups to isocyanate groups is 3.3:1. Araldite DY-D / CH as compound (BI) and MDI 1806 as compound (A) and LiCl as compound (C) To synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0170] 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) were charged into the reactor as described above. The reactor was closed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0171] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0172] like Figure 1 As can be seen in the IR spectrum, at 1749 cm -1 The characteristic signal of oxazolidinone carbonyl group was observed at

[0173] like Figure 1 As can be seen in Figure 2, no characteristic signals of isocyanurate groups were observed in the IR spectrum.

[0174] EEW was determined to be 250 g / eq.

[0175] Molecular weight analysis using GPC showed an average molecular weight of 533 g·mol -1 , and the polydispersity index is 3.42.

[0176] The color index was measured as 8.2 on the Gardner scale.

[0177] The viscosity of the product was measured to be 6720 mPa·s.

[0178] Example 2: According to the batch method, the molar ratio of epoxy groups to isocyanate groups was 3.9:1. Araldite DY 026 as compound (B-II) and MDI 1806 as compound (A) and LiCl as compound (C) To synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0179] LiCl (0.052 g, 1.23 mmol), MDI 1806 (10.3 g, 41 mmol) and Araldite DY 026 (35.6 g, 158 mmol BDDE) were charged into the reactor as described above. The reactor was closed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0180] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0181] In the IR spectrum, at 1749 cm -1 The characteristic signal of oxazolidinone carbonyl group was observed at

[0182] No characteristic signals of isocyanurate groups were observed in the IR spectrum.

[0183] EEW was determined to be 217 g / eq.

[0184] Molecular weight analysis using GPC showed an average molecular weight of 473 g·mol -1 , and the polydispersity index is 2.67.

[0185] The color index was measured as 7.4 on the Gardner scale.

[0186] The viscosity of the product was measured to be 1880 mPa·s.

[0187] Example 3: Using a semi-batch process with a molar ratio of epoxy groups to isocyanate groups of 3.3:1 Araldite DY / D-CH as compound (BI) and MDI 1806 as compound (A) and LiCl as compound (C) To synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0188] A reactor as described above was charged with LiCl (0.03 g, 0.7 mmol) and Araldite DY / D-CH (20.23 g, 84 mmol BDDE). The reactor was closed and inertized with argon. The mixture was stirred (400 rpm) and heated to 175°C. After 10 minutes at this temperature, MDI 1806 (6.25 g, 25 mmol) was added as compound (A) at a rate of 1 mL / min. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0189] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0190] In the IR spectrum, at 1749 cm -1 The characteristic signal of oxazolidinone carbonyl group was observed at

[0191] No characteristic signals of isocyanurate groups were observed in the IR spectrum.

[0192] EEW was determined to be 247 g / eq.

[0193] Molecular weight analysis using GPC showed an average molecular weight of 416 g·mol -1 , and the polydispersity index is 3.37.

[0194] The color index was measured as 9.1 on the Gardner scale.

[0195] The viscosity of the product was measured to be 4790 mPa·s.

[0196] Example 4: According to the batch method, the molar ratio of epoxy groups to isocyanate groups was 3.3:1. Araldite DY-D / CH was used as compound (BI) and in the presence of a mixture of o-dichlorobenzene and sulfolane of compound (D). Synthesis of epoxy-terminated polyoxazolidinone-based Prepolymer

[0197] Into the reactor as described above, 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), o-dichlorobenzene (8.3 ml) and sulfolane (2.5 ml) were loaded. The reactor was closed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0198] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0199] In the IR spectrum, at 1749 cm -1 The characteristic signal of oxazolidinone carbonyl group was observed at

[0200] No characteristic signals of isocyanurate groups were observed in the IR spectrum.

[0201] EEW was determined to be 322 g / eq.

[0202] To remove the solvent, the mixture was heated to 200°C, above the boiling point of o-DCB, for 5 hours. During this treatment, the sample became highly viscous and showed a deepening color.

[0203] Molecular weight analysis by GPC showed an average molecular weight of 508 g·mol before distillation. -1 The polydispersity index is 3.23, and the average molecular weight after distillation is 638 g·mol -1 And the polydispersity index is 6.0.

[0204] The color index was measured at 8.0 on the Gardner scale before distillation and 8.4 on the Gardner scale after distillation.

[0205] The viscosity of the product was measured to be 569 mPa·s before distillation and 74200 mPa·s after distillation.

[0206] Example 5 (Comparative): According to the batch method, a molar ratio of epoxy groups to isocyanate groups of 2.5:1 was used. Araldite DY / D-CH as compound (BI) and MDI 1806 as compound (A) and LiCl as compound (C) To synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0207] 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) were charged into the reactor as described above. The reactor was closed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0208] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0209] In the IR spectrum, at 1749 cm -1 The characteristic signal of oxazolidinone carbonyl group was observed at

[0210] No characteristic signals of isocyanurate groups were observed in the IR spectrum.

[0211] EEW was determined to be 323 g / eq.

[0212] Molecular weight analysis using GPC showed an average molecular weight of 581 g·mol -1 , and the polydispersity index is 3.78.

[0213] The color index was measured as 10.4 on the Gardner scale.

[0214] The viscosity of the product was measured to be 68600 mPa·s.

[0215] Example 6: Using a batch process with a molar ratio of epoxy groups to isocyanate groups of 1.7:1 Araldite DY / D-CH as compound (BI) and MDI 1806 as compound (A) and LiCl as compound (C) To synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0216] 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) were charged into the reactor as described above. The reactor was closed and inerted with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 minutes, the reaction was stopped due to solidification of the reaction mixture.

[0217] like Figure 2 As can be seen in the IR spectrum, at 1749 cm -1 The characteristic signal of the oxazolidinone carbonyl group was observed at 400 Å, as well as many other peaks representing by-products.

[0218] like Figure 2 As can be seen in the IR spectrum, at 1749 cm -1The characteristic signal of the oxazolidinone carbonyl group was observed at 1725 cm -1 The signal at 1705 cm -1 The signal at can be assigned to the carbonyl group of the formed isocyanurate.

[0219] EEW could not be determined.

[0220] Molecular weight analysis using GPC was not possible.

[0221] The color index was determined to be >18, thus outside the range of the Gardner scale.

[0222] Example 7 (Comparative): Using a batch process with a molar ratio of epoxy groups to isocyanate groups of 3.3:1 Araldite DY-D / CH as compound (BI) and MDI 1806 as compound (A) and DMC as compound (C) To synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0223] A reactor as described above 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 closed and inertized with argon. The mixture was stirred (400 rpm) and heated to 175°C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0224] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0225] like Figure 3 As can be seen in the IR spectrum, at 1749 cm -1 The characteristic signal of the oxazolidinone carbonyl group was observed at 1725 cm -1 The signal at 1705 cm -1 The signal at can be assigned to the carbonyl group of the formed isocyanurate.

[0226] EEW was determined to be 233 g / eq.

[0227] Molecular weight analysis using GPC showed an average molecular weight of 396 g·mol -1 , and the polydispersity index is 3.86.

[0228] The color index was measured as 9.0 on the Gardner scale.

[0229] The viscosity of the product was measured to be 3260 mPa·s.

[0230] Example 8 (Comparative): Using a batch process with a molar ratio of epoxy groups to isocyanate groups of 3.3:1 Araldite DY-D / CH as compound (BI) and MDI 1806 as compound (A) and DMC as compound (C)To synthesize epoxy-terminated polyoxazolidinone-based prepolymers (similar to Example 7, but using increased catalyst concentrations)

[0231] A reactor as described above 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 closed and inertized with argon. The mixture was stirred (400 rpm) and heated to 175°C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0232] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0233] like Figure 4 As can be seen in the IR spectrum, at 1749 cm -1 The characteristic signal of the oxazolidinone carbonyl group was observed at 1725 cm -1 The signal at 1705 cm -1 The signal at can be assigned to the carbonyl group of the formed isocyanurate.

[0234] EEW was determined to be 233 g / eq.

[0235] Molecular weight analysis using GPC showed an average molecular weight of 483 g·mol -1 , and the polydispersity index is 6.62.

[0236] Since the product sample was inhomogeneous and turbid, the color index could not be determined.

[0237] Since the product sample was too inhomogeneous, the viscosity of the product could not be determined.

[0238] Example 9: Using a batch process with a molar ratio of epoxy groups to isocyanate groups of 3.3:1 Araldite DY-D / CH as compound (BI) and MDI 1806 as compound (A) using tetraphenylphosphonium bromide as Compound (C) is used to synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0239] The reactor as described above was charged with Ph 4 PBr (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 closed and inertized with argon. The mixture was stirred (400 rpm) and heated to 175°C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0240] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0241] In the IR spectrum, at 1749 cm -1 The characteristic signal of oxazolidinone carbonyl group was observed at

[0242] EEW was determined to be 227 g / eq.

[0243] Molecular weight analysis using GPC showed an average molecular weight of 394 g·mol -1 , and the polydispersity index is 3.29.

[0244] The color index was measured as 9.0 on the Gardner scale.

[0245] The viscosity of the product was measured to be 4030 mPa·s.

[0246] Example 10: Using a batch process with a molar ratio of epoxy groups to isocyanate groups of 2.5:1 Araldite DY-D / CH as compound (BI) and MDI 1806 as compound (A) using tetraphenylphosphonium bromide as Compound (C) is used to synthesize epoxy-terminated polyoxazolidinone-based prepolymers

[0247] The reactor as described above was charged with Ph 4 PBr (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 closed and inertized with argon. The mixture was stirred (400 rpm) and heated to 175°C. After 3.5 hours, the reaction mixture was cooled to room temperature.

[0248] The absence of an isocyanate band (2260 cm -1 ) to confirm that the reaction is complete.

[0249] In the IR spectrum, at 1749 cm -1 The characteristic signal of the oxazolidinone carbonyl group was observed at 1725 cm -1 The signal at.

[0250] EEW was determined to be 370 g / eq.

[0251] Molecular weight analysis using GPC showed an average molecular weight of 662 g·mol -1 , and the polydispersity index is 4.55.

[0252] The color index was measured as 9.0 on the Gardner scale.

[0253] The viscosity of the product was measured to be 33000 mPa·s.

[0254]

Claims

1. A method for preparing epoxy-terminated polyoxazolidinones, comprising 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 catalyst (C) and optionally a solvent (D-1) having a boiling point above 170° C. at 1 bar; wherein the molar ratio of the epoxy group of the polyepoxide compound (B) to the isocyanate group of the polyisocyanate compound (A) is 2.8:1 to 5:1; wherein the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, LiI, MgCl2, MgBr2, MgI2, SmI3, Ph4PBr, Ph4PCl, Ph3(C6H4-OCH3)PBr, Ph3(C6H4-OCH3)PCl, Ph3(C6H4F)PCl and Ph3(C6H4F)PBr; wherein the catalyst (C) is used in a molar amount of 0.001 to 2.0 mol % based on the polyepoxide compound (B); Wherein if a solvent (D-1) is used in the method, the copolymerization is carried out under the condition that the weight percentage of the solvent (D-1) is less than 5 weight %, And wherein the polyepoxide compound (B) is an aliphatic polyepoxide compound (B-1).

2. The method according to claim 1, wherein the copolymerization is carried out in the absence of solvent (D-1) and any other solvent. 3 . The method according to claim 1 , wherein the polyisocyanate compound (A) is an aliphatic polyisocyanate compound (A-1). 4 . The method according to claim 1 , wherein the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2).

5. The method according to claim 1, wherein the catalyst (C) is at least one compound selected from the group consisting of LiCl, LiBr, LiI, Ph4PBr and Ph4PCl.

6. The process according to claim 1, wherein the catalyst (C) is used in a molar amount of ≥0.05 to ≤1.0 mol %, based on the polyepoxide compound (B).

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

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

9. The method according to claim 1, wherein the aliphatic polyepoxide compound (B-1) is selected from ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and mixtures thereof.

10. The method according to claim 3, wherein the aliphatic polyisocyanate compound (A-1) is selected from 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane, and mixtures thereof.

11. The method according to claim 4, wherein the aromatic polyisocyanate compound (A-2) is selected from 1,3- and 1,4-bis(isocyanatomethyl)benzene, 1,3- and 1,4-bis(2-isocyanatopropyl-2-yl)benzene, 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene, and mixtures thereof.

12. The method according to claim 1, wherein the copolymerization is carried out at a reaction temperature of ≥130°C to ≤280°C.

13. The method according to claim 12, wherein the copolymerization is carried out at a reaction temperature of ≥165°C to ≤195°C.

14. An epoxy-terminated polyoxazolidinone obtainable by the process according to any one of claims 1 to 13.

15. The epoxy-terminated polyoxazolidinone according to claim 14, wherein the epoxy equivalent weight of the epoxy-terminated polyoxazolidinone is from 100 g / eq to 5000 g / eq, and wherein the epoxy equivalent weight is measured using a Metrohm 888 Titrando using potentiometric hydrochloric acid titration, the epoxy sample is added to a 250 ml beaker, then mixed with tetrabutylammonium bromide in 64.5 g / L glacial acetic acid, and then the solution is titrated with 0.1 mol / L peracetic acid until after the equivalent point. 16 . The epoxy group-terminated polyoxazolidone according to claim 15 , wherein the epoxy group-terminated polyoxazolidone has an epoxy equivalent weight of 200 g / eq to 1500 g / eq.

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