Process for producing hydroxyl-terminated oxazolidinone compositions

Abstract

The present invention relates to a process for producing a hydroxyl-terminated oxazolidinone composition comprising the reaction of a polyisocyanate compound having two or more isocyanate groups with glycerol carbonate and optionally in a solvent wherein the molar ratio of compound (B) to isocyanate groups of polyisocyanate compound (A) is at least 1.5: 1, and wherein the process comprises a step in which a catalyst (C) is present. The invention also relates to the resulting hydroxyl-terminated oxazolidinones and to a process for the production of hydroxyl-terminated oxazolidinones by removal of solvent and / or unreacted glycerol carbonate.

Description

[0001] This invention relates to a method for producing hydroxyl-terminated oxazolidinone compositions, comprising reacting a polyisocyanate compound having two or more isocyanate groups with glycerol carbonate and optionally a solvent, wherein the molar ratio of the isocyanate groups of compound (B) to those of polyisocyanate compound (A) is at least 1.5:1, and wherein the method includes a step in which a catalyst (C) is present. The invention also relates to the resulting hydroxyl-terminated oxazolidinone and a method for producing hydroxyl-terminated oxazolidinones by removing the solvent and / or unreacted glycerol carbonate.

[0002] In Endo et al. (Tetrahedron Letters, 2021, Vol. 72, 153086), a bicyclic guanidine-catalyzed synthesis of 4-hydroxymethyl-2-oxazolidinone from glycidyl carbamate derivatives was disclosed. In a first step, glycidyl carbamate was reacted with various monoisocyanates (e.g., phenyl isocyanate), diisocyanates (e.g., 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate), and triisocyanates to form a glycidyl carbamate intermediate, which was then intramolecularly cyclized in acetone in the presence of a 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyst to form 4-hydroxymethyl-2-oxazolidinone. All products were 4-hydroxymethyl-2-oxazolidinones with 100% 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomers. Furthermore, despite using long reaction times and high catalyst loadings, only moderate yields of 4-hydroxymethyl-2-oxazolidinone were obtained for diisocyanates or triisocyanates.

[0003] The object of this invention is to determine a simple method for preparing hydroxyl-terminated oxazolidinone compositions and hydroxyl-terminated oxazolidinones, wherein the regioselectivity of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer (4-Oxa) relative to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer (5-Oxa) can be modified. By adjusting the selectivity of 5-Oxa relative to 4-Oxa, the melting point of the resulting purified hydroxyl-terminated oxazolidinone should also be controlled, preferably increased. In particular, NCO reactive compounds with higher storage stability and better availability, and lower toxicity and thermal volatility should be used. Furthermore, the yield of polyisocyanate-based hydroxyl-terminated oxazolidinones should be improved, wherein the reaction time and the necessary amount of catalyst should be reduced simultaneously.

[0004] Surprisingly, it has been found that the above-mentioned technical problem can be solved by a method for producing hydroxyl-terminated oxazolidinone compositions, the method comprising reacting a polyisocyanate compound (A) having two or more isocyanate groups with a compound (B) and optionally in a solvent (D), wherein the compound (B) is a glycerol carbonate, and wherein the molar ratio of the isocyanate groups of the compound (B) to those of the polyisocyanate compound (A) is at least 1.5:1, and wherein the method includes a step in which a catalyst (C) is present.

[0005] As used herein, the term "oxazolidinone" is intended to refer to a compound that contains at least one oxazolidinone group in its molecule.

[0006] The term "hydroxyl-terminated" oxazolidinone refers to an oxazolidinone compound having at least one, preferably at least two, more preferably two to three terminal hydroxyl groups, and most preferably two hydroxyl groups.

[0007] As used herein, the term "oxazolidinone composition" is intended to mean a composition comprising a hydroxyl-terminated oxazolidinone, unreacted glyceryl carbonate (if used in stoichiometric excess), and solvent (D) (if solvent (D) is present).

[0008] All embodiments of the present invention can be combined unless the logical teachings clearly indicate that the embodiments cannot be combined.

[0009] As used herein, the term "polyisocyanate compound" is intended to refer to a compound having two or more isocyanate groups.

[0010] In one embodiment of the method according to the invention, 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).

[0011] In one embodiment of the method according to the invention, the polyisocyanate compound (A) is at least one polyisocyanate that can be obtained by various means, such as by phosgenation in the liquid or gas phase or by a phosgene-free route, such as by thermal urethane cracking.

[0012] In one embodiment of the method according to the invention, the polyisocyanate compound (A) is at least one compound selected from polyisocyanates having an isocyanate group having an aliphatic and / or aromatic bond and a molecular weight range of 140 g / mol to 600 g / mol, examples being 1,4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2-methyl-1,5-pentane diisocyanate, 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-hexane diisocyanate, 1,8-octane diisocyanate, 1,10-decane diisocyanate, and 1,12-dodecane diisocyanate. Esters, 1,3- and 1,4-cyclohexane diisocyanates, 1,3- and 1,4-bis(isocyanate methyl)cyclohexane, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12-MDI), 4,4'-diisocyanate-2,2-dicyclohexylpropane, 1-isocyanate-1-methyl-4(3)isocyanate methylcyclohexane, bis(isocyanate methyl)norbornene, or as exemplified by J. Prakt. Chem. 336 (1994) 185 -200, DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641380, 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 339396 and EP-A 0 798 Any polyisocyanate having a structure of urea diketone, isocyanurate, urethane, biuret, iminooxadiazine diketone and / or oxadiazine triketone, or a mixture of at least two such polyisocyanates, prepared by modification of simple aliphatic diisocyanates, such as those of the types described above, and 1,3- and 1,4-bis(isocyanate methyl)benzene (phenylenedimethyl diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanate propyl-2-yl)benzene (tetramethylphenylenedimethyl diisocyanate). Methyl diisocyanate (TMXDI), 1,3-bis(isocyanate methyl)-4-methylbenzene, 1,3-bis(isocyanate methyl)-4-ethylbenzene, 1,3-bis(isocyanate methyl)-5-methylbenzene, 1,3-bis(isocyanate methyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanate methyl)-4,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,3,5-dimethylbenzene,6-Tetramethylbenzene, 1,3-bis(isocyanate methyl)-5-tert-butylbenzene, 1,3-bis(isocyanate methyl)-4-chlorobenzene, 1,3-bis(isocyanate methyl)-4,5-dichlorobenzene, 1,3-bis(isocyanate methyl)-2,4,5,6-tetrachlorobenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetrabromobenzene, 1,4-bis(2-isocyanate ethyl)benzene and 1, 4-Bis(isocyanate methyl)naphthalene, 1,2-, 1,3- and 1,4-diisocyanate phenylene (phenylene diisocyanate), 2,4- and 2,6-diisocyanate toluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanate phenylene, isomeric diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, diisododecylphenylene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2, 4'- and 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, diethylene glycol diphenyl ether diisocyanate, 1,3-propanediol diphenyl ether diisocyanate, benzophenone diisocyanate, benzene triisocyanate, 2,4,6-toluene triisocyanate, trimethylbenzene triisocyanate, diphenylmethane Alkane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, isonaphthalene triisocyanate and methylnaphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanate-1-[(5-isocyanate-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'-pentaisocyanate, and polynuclear homologues of diphenylmethane diisocyanates known as "polymer-MDI", as well as monomers of 2,4- and / or 2,6-TDI can be obtained by reacting with polyols and / or oligomerizing, preferably trimerizing, polyisocyanates having urethane and / or isocyanurate structures, which can be obtained through, for example, DE-A 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546 399, CN 105218780, CN103881050, CN 101717571, US 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915 or JP Obtained by any known method described in 56059828, or a mixture of at least two such polyisocyanates, and those polyisocyanate compounds with aromatic and aliphatic isocyanate groups, such as mixed trimers or urethane esters 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 0807 623.

[0013] More preferably, the polyisocyanate compound (A) is at least one compound selected from polyisocyanates having aliphatic and / or aromatic isocyanate groups with a molecular weight ranging from 140 g / mol to 600 g / mol, examples being 1,4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-hexane diisocyanate, and 1,8-octane diisocyanate. 1,3- and 1,4-cyclohexane diisocyanates, 1,3- and 1,4-bis(isocyanate methyl)cyclohexane, 1-isocyanate methyl-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-dicyclohexylmethane diisocyanates (H12-MDI), 4,4'-diisocyanate methyl-2,2-dicyclohexylpropane, or as shown in example J. Prakt. Chem. 336 (1994) 185 - 200, 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 EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 As described in 798299, any polyisocyanate having the structure of urea dione, isocyanurate, urethane, biuret, iminooxadiazine dione, and / or oxadiazine trione is prepared by modification of simple aliphatic diisocyanates, such as those of the types described above, and 1,3- and 1,4-bis(isocyanate methyl)benzene (phenylenediethylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanate propyl-2-yl)benzene (tetramethylphenylenediethylene diisocyanate, TMXDI), 1,3-bis(isocyanate methyl)-4-methylbenzene, 1,3-bis(isocyanate methyl)-4-ethylbenzene, 1 3-Bis(isocyanate methyl)-5-methylbenzene, 1,3-bis(isocyanate methyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanate methyl)-4,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanate methyl)-5-tert-butylbenzene, 1,4-bis(2-isocyanate ethyl)benzene, 1,4-bis(isocyanate methyl)naphthalene, 1,2-, 1,3- and 1,4-diisocyanate benzene (phenyl diisocyanate), 2,4- and 2,6-Diisocyanate toluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanate benzene, diisopropylbenzene diisocyanate, diisododecylbenzene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propanediol diphenyl ether diisocyanate Cyanides, benzene triisocyanates, 2,4,6-toluene triisocyanates, trimethylbenzene triisocyanates, 3-methyldiphenylmethane-4,6,4'-triisocyanates, isonaphthalene triisocyanates and methylnaphthalene diisocyanates, triphenylmethane triisocyanates, 2,4-diisocyanate-1-[(5-isocyanate-2-methylphenyl)methyl]benzene, and polynuclear homologues of diphenylmethane diisocyanates known as "polymer-MDI", as well as polyisocyanates having urethane and / or isocyanurate structures obtainable from monomers 2,4- and / or 2,6-TDI through reaction with polyols and / or oligomerization, preferably trimerization, which can be obtained, for example, through DE-A Obtained by any known method as described in JP 63260915 or JP56059828, and those polyisocyanate compounds with aromatic and aliphatic isocyanate groups, such as DE-A 1 670 667, EP-A 0 078 991, 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 JP56059828, and those polyisocyanate compounds such as DE-A 1 670 667, EP-A 0 078 991, EP-A 0 Mixed trimers or urethane esters of 2,4- and / or 2,6-TDI with HDI as described in 696 606 and EP-A 0 807 623.

[0014] Most preferably, the polyisocyanate compound (A) is at least one compound selected from polyisocyanates having a molecular weight range of 140 g / mol to 600 g / mol and having an aliphatic and / or aromatic isocyanate group, examples being 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 1-isocyano-3,3,5-trimethyl-5-isocyano-methylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12-MDI), and 1,3 - and 1,4-bis(isocyanate methyl)benzene (phenylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanate prop-2-yl)benzene (tetramethylphenylene diisocyanate, TMXDI), 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylethane diisocyanate, 1,5-naphthalene diisocyanate (NDI).

[0015] A mixture of two or more of the above-mentioned polyisocyanate compounds (A) may also be used.

[0016] As used herein, the term "aliphatic polyisocyanate compound" is intended to refer to a compound having two or more isocyanate groups and an aliphatic moiety and may contain an aromatic moiety. Aliphatic polyisocyanate compounds refer to linear aliphatic or alicyclic polyisocyanate compounds. In aliphatic polyisocyanate compounds, the isocyanate moiety is not directly bonded to the aromatic moiety. Diphenylmethylene diisocyanate (XDI) is an example of an aliphatic polyisocyanate having an isocyanate moiety not directly bonded to the aromatic moiety, wherein the isocyanate group is bonded to the phenyl group via a methylene group. In a preferred embodiment of the method according to the invention, the polyisocyanate compound (A) is aliphatic (A-1).

[0017] In one embodiment of the method according to the invention, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from polyisocyanates having aliphatic bonded isocyanate groups with a molecular weight range of 140 g / mol to 400 g / mol, examples being 1,4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2-methyl-1,5-pentane diisocyanate, 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-hexane diisocyanate, 1,8-octane diisocyanate, 1,10-decane diisocyanate, 1,12-dodecane diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, etc. Hexane diisocyanate, 1,3- and 1,4-bis(isocyanate methyl)cyclohexane, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12-MDI), 4,4'-diisocyanate-2,2-dicyclohexylpropane, 1-isocyanate-1-methyl-4(3)isocyanate methylcyclohexane, bis(isocyanate methyl)norbornene, 1,3- and 1,4-bis(isocyanate methyl)benzene (phenylenedimethyl diisocyanate) Ester, XDI), 1,3- and 1,4-bis(2-isocyanate prop-2-yl)benzene (tetramethylphenyl diisocyanate, TMXDI), 1,3-bis(isocyanate methyl)-4-methylbenzene, 1,3-bis(isocyanate methyl)-4-ethylbenzene, 1,3-bis(isocyanate methyl)-5-methylbenzene, 1,3-bis(isocyanate methyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanate methyl)-4,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,5-dimethylbenzene, 1,4-bis(isocyanate methyl) -2,3,5,6-Tetramethylbenzene, 1,3-bis(isocyanate methyl)-5-tert-butylbenzene, 1,3-bis(isocyanate methyl)-4-chlorobenzene, 1,3-bis(isocyanate methyl)-4,5-dichlorobenzene, 1,3-bis(isocyanate methyl)-2,4,5,6-tetrachlorobenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetrabromobenzene, 1,4-bis(2-isocyanate ethyl)benzene and 1,4-bis(isocyanate methyl)naphthalene, or as exemplified by J. Prakt. Chem.336 (1994) 185-200, DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928503 or EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299, any polyisocyanate having a structure of ureidone, isocyanurate, urethane, biuret, iminooxadiazine dione and / or oxadiazine trione, prepared by modification of simple aliphatic diisocyanates, such as those of the above types.

[0018] More preferably, the aliphatic polyisocyanate compound (A-1) is at least one compound selected from polyisocyanates having an aliphatic bonded isocyanate group and a molecular weight range of 140 g / mol to 400 g / mol, examples being 1,4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-hexane diisocyanate, 1,8-octane diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, 1,3- and 1,4-bis(isocyanate) 1-Isocyanate-3,3,5-trimethyl-5-isocyanate-methylcyclohexane (isophorone diisocyanate, IPDI), 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12-MDI), 4,4'-diisocyanate-2,2-dicyclohexylpropane, 1,3- and 1,4-bis(isocyanate-methyl)benzene (phenylenediethylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanate-propyl-2-yl)benzene (tetramethylphenylenediethylene) 1,3-Bis(isocyanate methyl)-4-methylbenzene, 1,3-bis(isocyanate methyl)-4-ethylbenzene, 1,3-bis(isocyanate methyl)-5-methylbenzene, 1,3-bis(isocyanate methyl)-2,4,6-trimethylbenzene, 1,3-bis(isocyanate methyl)-4,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,5-dimethylbenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetramethylbenzene, 1,3 -bis(isocyanate methyl)-5-tert-butylbenzene, 1,3-bis(isocyanate methyl)-4-chlorobenzene, 1,3-bis(isocyanate methyl)-4,5-dichlorobenzene, 1,3-bis(isocyanate methyl)-2,4,5,6-tetrachlorobenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanate methyl)-2,3,5,6-tetrabromobenzene, 1,4-bis(2-isocyanate ethyl)benzene and 1,4-bis(isocyanate methyl)naphthalene, or as exemplified by J. Prakt. Chem.336(1994) 185-200, 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 structure of ureidone, isocyanurate, urethane, biuret, iminooxadiazine dione and / or oxadiazine trione, or a mixture of at least two such polyisocyanates, prepared by modification of simple aliphatic diisocyanates, such as those of the above types. .

[0019] Most preferably, the aliphatic polyisocyanate compound (A-1) is one or more compounds selected from 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI) and 1-isocyano-3,3,5-trimethyl-5-isocyano-methylcyclohexane (isophorone diisocyanate, IPDI).

[0020] A mixture of two or more of the above-mentioned aliphatic polyisocyanate compounds (A-1) may also be used.

[0021] As used herein, the term "aromatic polyisocyanate compound" is intended to mean a compound having two or more isocyanate groups and must contain an aromatic moiety and may additionally contain an aliphatic moiety. Therefore, the term "aromatic polyisocyanate compound" is intended to mean a compound having two or more isocyanate groups directly bonded to an aromatic moiety, such as 2,4- and 2,6-diisocyanate toluene (toluene diisocyanate, TDI) or 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI). In a less preferred embodiment of the method according to the invention, the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2).

[0022] In a preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound selected from compounds with a molecular weight range of 160 g / mol to 600 g / mol. Aromatic diisocyanates and triisocyanates at g / mol, such as 1,2-, 1,3- and 1,4-diisocyanate phenylene (phenylene diisocyanate), 2,4- and 2,6-diisocyanate toluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanate phenylene, diisopropylbenzene diisocyanate, diisododecylbenzene diisocyanate and biphenyl diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenyl ether diisocyanate, etc. Isocyanates, ethylene glycol diphenyl ether diisocyanate, 1,3-propanediol diphenyl ether diisocyanate, benzene triisocyanate, 2,4,6-toluene triisocyanate, trimethylbenzene triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, isonaphthalene triisocyanate and methylnaphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanate-1-[(5-isocyanate-2-methylphenyl)methyl]benzene, and polynuclear homologues of diphenylmethane diisocyanates known as "polymer-MDI", as well as polyisocyanates having urethane and / or isocyanurate structures obtainable from monomers 2,4- and / or 2,6-TDI through reaction with polyols and / or oligomerization, preferably trimerization, which can be obtained, for example, through DE-A Obtained by any known method described in 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546399, CN 105218780, CN 103881050, CN 101717571, US 3 183 112, EP-A 0 416 338, EP-A 0751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915, or JP 56059828.

[0023] In a more preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound selected from aromatic diisocyanates and triisocyanates with a molecular weight range of 160 g / mol to 600 g / mol, such as 1,2-, 1,3- and 1,4-diisocyanate phenylene (phenylene diisocyanate), 2,4- and 2,6-diisocyanate toluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-1,4-diisocyanate phenylene, isomeric diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, diisododecylphenylene diisocyanate, and biphenyl diisocyanate. Cyanide esters, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, diethylene glycol diphenyl ether diisocyanate 1,3-Propanediol diphenyl ether diisocyanate, benzophenone diisocyanate, benzene triisocyanate, 2,4,6-toluene triisocyanate, trimethylbenzene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, isonaphthalene triisocyanate and methylnaphthalene diisocyanate, triphenylmethane triisocyanate, 2,4-diisocyanate oxy-1-[(5-isocyanate) [2-methylphenyl]methylbenzene, 4-methyldiphenylmethane-3,5,2',4',6'-pentaisocyanate, and polynuclear homologues of diphenylmethane diisocyanate known as "polymer-MDI", as well as polyisocyanates having urethane and / or isocyanurate structures obtainable from monomers 2,4- and / or 2,6-TDI through reaction with polyols and / or oligomerization, preferably trimerization, which can be obtained, for example, through DE-A Obtained by any known method described in 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546 399, CN 105218780, CN 103881050, CN 101717571, US 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1378 529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915 or JP 56059828, or a mixture of at least two such polyisocyanates.

[0024] In a further preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound selected from 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), and 2,4- and 2,6-toluene diisocyanate (TDI).

[0025] Most preferably, the aromatic polyisocyanate compound (A-2) is at least one compound selected from 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate.

[0026] A mixture of two or more aromatic polyisocyanate compounds (A-2) can also be used.

[0027] Glyceryl carbonate is compound (B) according to the present invention.

[0028] In a preferred embodiment of the invention, the molar ratio of the isocyanate groups of compound (B) to polyisocyanate compound (A) is 1.5:1 to 7.0:1, preferably 1.8:1 to 6.0:1, more preferably 1.9:1 to 5.5:1, and most preferably 2.0:1 to 5.0:1. If the molar ratio of the isocyanate groups of compound (B) to polyisocyanate compound (A) is less than 1.5:1, the viscosity of the resulting hydroxyl-terminated oxazolidinone composition containing the hydroxyl-terminated oxazolidinone increases significantly; if the molar ratio is greater than 7.0:1, a higher amount of glyceryl carbonate needs to be removed.

[0029] In one embodiment of the method according to the invention, the catalyst (C) is present in a molar amount of 0.001 to 2.0 mol% based on the polyisocyanate compound (A), preferably 0.001 to 2.0 mol%, more preferably 0.01 to ≤ 1.5 mol%, and more preferably ≥ 0.05 to ≤ 1.3 mol%. If a catalyst amount below 0.001 mol% is used, the conversion rate decreases, while a catalyst amount above 2.0 mol% leads to the formation of byproducts.

[0030] In a preferred embodiment of the invention, the catalyst (C) is a Lewis base and / or a Brønsted base, such as substituted or unsubstituted ammonium halides, substituted or unsubstituted phosphonium halides, amines, metal hydroxides, metal carbonates, metal alkoxides, metal acetates, metal formates, metal molybdates, metal vanadates, and / or metal phosphates.

[0031] In a more preferred embodiment of the present invention, the catalyst (C) is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,4-diazabicyclo[2.2.2]octane (DABCO), imidazole, 1-methylimidazolium, 2-methylimidazolium, 4(5)-methylimidazolium, 2,4(5)dimethylimidazolium, 1-ethylimidazolium, 2-ethylimidazolium, 1-phenylimidazolium, 2-phenylimidazolium, 4(5)phenylimidazolium, N,N -Dimethylaminopyridine, guanidine, 1,1,3,3,-tetramethylguanidine (TMG), pyridine, 1-Azanaphthaline (Chinolin), N-methylpiperidine, N -Methylmorpholine, N,N '-Dimethylpiperazine, N,N - Dimethylaniline, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)chloroimine, tetraphenylphosphonium nitrate, and tetraphenylphosphonium carbonate, preferably 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, 1,1,3,3,-tetramethylguanidine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene, more preferably at least one compound of 1,1,3,3,-tetramethylguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0032] The use of 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, 1,1,3,3,-tetramethylguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene, preferably 1,1,3,3,-tetramethylguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene as catalysts (C) results in improved reactivity and higher conversion rates in the reaction process.

[0033] In one embodiment, the reaction is carried out in solvent (D).

[0034] In one embodiment of the invention, the total of diisocyanate compound (A), compound (B) and catalyst (C) is calculated to a mass ratio of 40% to 100% by weight, preferably 50% to 90% by weight, and more preferably 60% to 80% by weight, relative to the total of diisocyanate compound (A), compound (B), catalyst (C) and solvent (D).

[0035] Solvent (D) is defined in accordance with the general definition as a substance that dissolves the solute, namely compound (A) and / or compound (B) and / or compound (C) but does not react with compound (A), compound (B) and / or catalyst (C), especially polyisocyanate compound (A) (chemical).

[0036] The suitable solvent (D) according to the invention is a solvent with a boiling point at 1 bar (absolute) equal to or below 200°C, preferably equal to or below 190°C, and more preferably equal to or below 180°C.

[0037] In a preferred embodiment of the invention, the reaction is carried out in the presence of a solvent (D), wherein the solvent (D) is one or more compounds selected from chlorobenzene, different isomers of dichlorobenzene, dimethylformamide, etc. N,N -Dimethylacetamide, tetrahydrofuran, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1-methoxy-2-(2-methoxyethoxy)ethane, cyclohexanone, benzyl nitrile, methyl isobutyl ketone and different isomers of dioxane, preferably acetone, cyclohexanone, benzyl nitrile and methyl isobutyl ketone.

[0038] The reaction according to the invention is carried out in the absence of a solvent (E) with a boiling point above 200°C, preferably above 190°C, and more preferably above 180°C at 1 bar (absolute).

[0039] Such solvents (E) include, for example, cyclic carbonates, such as ethylene carbonate or propylene carbonate. N -Methylpyrrolidone (NMP) and sulfolane. The absence of such solvents reduces the energy-intensive and time-consuming removal processes of these high-boiling-point solvents, such as distillation.

[0040] The absence of additional solvent (E) means that the amount of solvent (E) is less than 5% by weight, preferably 4% by weight, and more preferably 2% by weight.

[0041] In one embodiment of the invention, the reaction temperature of the one-step process is ≥ 20°C to ≤ 180°C, preferably ≥ 40°C to ≤ 160°C, and more preferably ≥ 60°C to ≤ 140°C.

[0042] In one embodiment of the invention, the reaction time of the one-step method is 10 minutes to 8 hours, preferably 1 hour to 6 hours, and more preferably 2 hours to 4 hours.

[0043] In one embodiment of the present invention, the method further includes: a) Polyisocyanate compound (A) and compound (B) are mixed and reacted at a reaction temperature T1, optionally in solvent (D), to form an intermediate (F) containing urethane groups. b) In the presence of catalyst (C) at a reaction temperature T2, the intermediate (F) containing a carbamate group is decarboxylated to form a hydroxyl-terminated oxazolidinone composition.

[0044] In a less preferred embodiment of the present invention, method step a) includes: a-1) Mixing polyisocyanate compound (A) and compound (B), optional catalyst (C), and optional solvent (D) to provide mixture (G), a-2) React the mixture (G) at a reaction temperature T1 to form an intermediate (F) containing urethane groups.

[0045] In an alternative, less preferred embodiment of the invention, method step a) includes: ai) Mixing a polyisocyanate compound (A), an optional catalyst (C), and an optional solvent (D) to provide a mixture (H), a-ii) Compound (B) is added to mixture (H) at reaction temperature T1 to form intermediate (F) containing urethane groups.

[0046] In yet another alternative preferred embodiment of the invention, method step a) includes: (aI.) A mixture of compound (B), optional catalyst (C), and optional solvent (D) to provide mixture (I), a-II.) At a reaction temperature T1, a polyisocyanate compound (A) is added to a mixture (I) to form an intermediate (F) containing a carbamate group.

[0047] For safety reasons, it is preferable to add the polyisocyanate compound (A) to the mixture (I) in step a-II.) in the latter case.

[0048] In one embodiment of the method of the present invention, the reaction temperature T1 in step a) is equal to the reaction temperature T2 in step b) (T1 = T2), or the reaction temperature T1 in step a) is lower than the reaction temperature T2 in step b) (T1 = T2). <T2)。

[0049] In one embodiment of the invention, T2 in step b) is ≥ 80°C to ≤ 290°C, preferably ≥ 90°C to ≤ 180°C, and more preferably ≥ 100°C to ≤ 160°C.

[0050] In the first preferred embodiment (1) of the present invention, the method further includes: a) Polyisocyanate compound (A) and compound (B), catalyst (C), and optionally solvent (D) are mixed and reacted at reaction temperature T1 to form an intermediate (F) containing urethane groups and cyclic carbonate groups. b) In the presence of catalyst (C), the intermediate (F) containing a carbamate group is decarboxylated at a reaction temperature T2 to form a hydroxyl-terminated oxazolidinone composition, wherein T1 <T2。

[0051] In a preferred embodiment of the first preferred embodiment (1) of the present invention, T1 in step a) is ≥20°C to ≤180°C, preferably ≥20°C to ≤130°C, and more preferably ≥20°C to ≤60°C.

[0052] In a preferred embodiment of the invention, T2 in step b) is ≥ 80°C to ≤ 290°C, preferably ≥ 90°C to ≤ 180°C, and more preferably ≥ 100°C to ≤ 160°C. If T2 in step b) is higher than 290°C, an increased decomposition rate of the hydroxyl-terminated oxazolidinone composition is observed. If T2 is lower than 80°C, the decarboxylation rate decreases, resulting in a lower conversion rate.

[0053] In a preferred embodiment of the first preferred embodiment (1) of the present invention, if an aromatic polyisocyanate compound (A-2) is used, step a) is carried out, particularly in the presence of a solvent (D), to form a solid intermediate (F) containing urethane groups at the reaction temperature.

[0054] In an alternative preferred embodiment within the first preferred embodiment (1) of the invention, step a) is solvent-free (D), wherein solvent (D) is preferably avoided for aliphatic polyisocyanate compounds (A-2), such as HDI and IPDI, wherein the aliphatic polyisocyanate compound (A-1) forms a processable, liquid, stirable intermediate (F) containing urethane groups at the reaction temperature.

[0055] In a preferred embodiment of the first preferred embodiment (1) of the present invention, the reaction time t1 in step a) is 10 minutes to 8 hours, preferably 1 hour to 7 hours, and more preferably 2 hours to 6 hours. If the reaction time t1 is less than 10 minutes, the conversion rate to the intermediate (F) containing the urethane group decreases, while a long reaction time of more than 8 hours increases the formation of side reactions and / or oligomers in subsequent reactions.

[0056] In a preferred embodiment of the first preferred embodiment (1) of the present invention, the reaction time t2 in step b) is 10 minutes to 8 hours, preferably 1 hour to 6 hours, more preferably 2 hours to 4 hours. If the reaction time t2 is less than 10 minutes, the conversion rate to the hydroxyl-terminated oxazolidinone composition decreases, while a long reaction time of more than 8 hours increases the formation of side reactions and / or oligomers in subsequent reactions.

[0057] In a second preferred embodiment (2) of the present invention, the method further includes: a) At a reaction temperature T1, in the absence of a catalyst (C) and optionally in a solvent (D), a polyisocyanate compound (A) and a compound (B) are mixed and reacted to form an intermediate (F) containing urethane groups comprising cyclic carbonate groups. b) In the presence of catalyst (C), the intermediate (F) containing urethane groups is decarboxylated at a reaction temperature T2 to form a hydroxyl-terminated oxazolidinone composition, wherein T1 = T2.

[0058] In a preferred embodiment of the second preferred embodiment (2) of the present invention, T1 in step a) and T2 in step b) are ≥ 80°C to ≤ 290°C, preferably ≥ 90°C to ≤ 180°C, and more preferably ≥ 100°C to ≤ 160°C. If T2 in step b) is higher than 290°C, an increased decomposition rate of the hydroxyl-terminated oxazolidinone composition is observed. If T2 is lower than 80°C, the decarboxylation rate decreases, resulting in a decrease in conversion.

[0059] In a preferred embodiment of the second preferred embodiment (2) of the present invention, if an aromatic polyisocyanate compound (A-2) is used, step a) is carried out, particularly in the presence of a solvent (D), to form a solid intermediate (F) containing urethane groups at the reaction temperature.

[0060] In an alternative preferred embodiment of the second preferred embodiment (2) of the invention, step a) is solvent-free (D), wherein solvent (D) is preferably avoided for aliphatic polyisocyanate compounds (A-2), such as HDI and IPDI, wherein the aliphatic polyisocyanate compound (A-1) forms a processable, liquid, stirable intermediate (F) containing urethane groups at the reaction temperature.

[0061] In a preferred embodiment of the second preferred embodiment (2) of the present invention, the reaction time t1 in step a) is from 10 minutes to 8 hours, preferably from 1 hour to 7 hours, and more preferably from 2 hours to 6 hours. If the reaction time t1 is less than 10 minutes, the conversion to the urethane-containing intermediate (F) decreases, while a long reaction time of more than 8 hours increases the formation of side reactions and / or oligomers in subsequent reactions. According to the present invention, the reaction time is defined as the sum of the addition time of at least one reactant and the subsequent reaction time, wherein the reaction mixture is stirred and reacted.

[0062] In a preferred embodiment of the second preferred embodiment (2) of the present invention, the reaction time t2 in step b) is 10 minutes to 8 hours, preferably 1 hour to 6 hours, more preferably 2 hours to 4 hours. If the reaction time t2 is less than 10 minutes, the conversion rate to the hydroxyl-terminated oxazolidinone composition decreases, while a long reaction time of more than 8 hours increases the formation of side reactions and / or oligomers in subsequent reactions.

[0063] Another subject of the present invention is a hydroxyl-terminated oxazolidinone composition obtainable according to the method of the present invention.

[0064] In one embodiment of the invention, the molar ratio of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer of the hydroxyl-terminated oxazolidinone composition is >0.0:1 to ≤100.0:1, preferably ≥0.1 to ≤20.0:1, more preferably ≥0.2:1 to ≤5.0:1, wherein the molar ratio of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer is estimated according to the NMR measurement method disclosed in the experimental section.

[0065] Another subject of the invention is a method for producing hydroxyl-terminated oxazolidinones, wherein a solvent (D) and / or compound (B) are removed from a hydroxyl-terminated oxazolidinone composition obtained according to the method of the invention or a hydroxyl-terminated oxazolidinone composition obtainable according to the method of the invention. Removal of the solvent (D) and / or glyceryl carbonate as unreacted compound (B) may be beneficial for future polymerization applications, as halogenated solvents and / or unreacted glyceryl carbonate may interfere with these polymerization reactions and negatively affect the resulting polymer products.

[0066] In one embodiment of the invention, unreacted compound (B) and / or solvent (D) are removed by heat treatment, preferably by distillation and / or by extraction, and more preferably by thin-film evaporation.

[0067] Another subject of the present invention is hydroxyl-terminated oxazolidinones obtainable according to the method of the present invention.

[0068] In one embodiment of the invention, the molar ratio of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer of the hydroxyl-terminated oxazolidinone is >0.0:1 to ≤100.0:1, preferably ≥0.1 to ≤20.0:1, more preferably ≥0.2:1 to ≤5.0:1, wherein the molar ratio of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer is estimated by the NMR measurement method disclosed in the experimental section. Example

[0069] The invention is further described with reference to the following embodiments, but is not intended to be limited thereto.

[0070] Compound (A) AI: MDI, diphenylmethane diisocyanate (MDI 44), purity >99%, Covestro AG, Germany.

[0071] Compound (B) To calculate the experimental molar ratio, the compound is assumed to be 100% pure. This calculation ignores possible impurities, such as alcohols.

[0072] BI: Glycerin, see Endo et al. for details.

[0073] B-II: Glyceryl carbonate, purity >95%, UBE Corporation Europe, Spain.

[0074] Catalyst (C) CI: Triazabicyclodecene (TBD), 98% purity, Sigma Aldrich. The concentration of the catalyst is given in ppm relative to the theoretical mass of the monomer used.

[0075] Solvent (D) DI: Acetone. Purity >99%, Fisher Scientific. D-II: Dichloromethane, see Endo et al. for details.

[0076] All chemicals were used as is without further purification.

[0077] Characterization of oxazolidinone NMR NMR measurements were recorded using a Bruker AV III 600 NMR instrument: 1 H: 80 MHz or 400 MHz, at 293 K. Calibrate the spectra to their respective solvent peaks: 1 H: 2.50 ppm (DMSO-d6). Chemical shift (δ) is expressed in ppm. NMR spectra were evaluated using a MestReNova from Mestrelab Research, SL. The isomer ratio between 4-Oxa and 5-Oxa was determined by integrating the proton signal of the methylene bridge between the aromatic rings of the two isomers in comparison.

[0078] DSC The thermal properties of oxazolidinones were characterized by dual scanning calorimetry (DSC). Measurements were performed on a Mettler Toledo DSC 3+ / 500. Samples (6 to 15 mg) were weighed into a capped 40 μL Alox dish and heated from -40 °C to 170 °C at a heating rate of 10 K / min in three cycles under an argon flow (80 mL / min), with each holding phase lasting 10 min. The second heating cycle was used to assess the melting point (T0). m For melting point, the peak minimum was determined. For data analysis, the STAR software was used. e SW 16.30.

[0079] reactor The reaction was carried out in a 500 mL four-necked round-bottom flask equipped with a glass reflux condenser, a gas inlet (N2), a syringe pump (SyrDos IP-SYRDOS2-HP-XLP), a glass inlet tube with a temperature probe (Ebro GFX 460), and a top-mounted KPG stirrer (IKA RW20). The round-bottom flask was heated with a Winkler heating shroud (WM / BRI / 250, maximum heating capacity 120 W), which was connected to the temperature probe via an Ebro RB 1691 BS.

[0080] Example 1 (Comparative): In a two-step reaction procedure, using TBD with an isocyanate group / hydroxyl molar ratio of 1:2. (CI) as compound (C) and solvent dichloromethane (D-II), with MDI 44 as compound (AI) and glycidyl as Synthesis of hydroxyl-terminated oxazolidinone compounds (BI) The synthetic data are applicable to the synthetic data disclosed in paragraphs 4-3 and 4-4 on pages S9 and S10 of Endo et al., Tetrahedron Letters, 2021, Vol. 72, 153086, and particularly the supporting information.

[0081] Example 2: In a two-step reaction procedure, using TBD (C-) at an isocyanate group / hydroxyl molar ratio of 1:2.1. I) as compound (C) and solvent acetone (DI), using MDI 44 as compound (AI) and glyceryl carbonate as compound (B-II) Synthesis of hydroxyl-terminated oxazolidinone groups Glyceryl carbonate (126.97 g, 1.06 mol) (B-II) and TBD (0.70 g, 5.00 mmol) (CI) were loaded into the reactor as described above. Acetone (200 mL) (DI) was then added, and the mixture was stirred (200–300 rpm) and purged with a constant stream of nitrogen throughout the reaction. The reaction was carried out at room temperature. MDI 44 (125.13 g, 0.50 mol) (AI) was dissolved in acetone (240 mL) and added continuously over a 60-minute time interval using a syringe pump, flushing the pump with acetone (40 mL) after each monomer addition. The reaction was then stirred for another 60 minutes. The solvent was removed under vacuum, and the urethane-containing intermediate product was vacuum-dried at 50 °C for 12 hours.

[0082] The dried carbamate-containing intermediate product was added to a clean reaction vessel, and the mixture was stirred (200-300 rpm) and purged with a constant stream of nitrogen throughout the reaction. The reaction was carried out in the vessel at 140 °C. The reaction was then stirred and heated for an additional 180 minutes, after which the hot reaction mixture was drained. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate).

[0083] During the reaction, a sample of the reaction mixture was extracted and analyzed by infrared spectroscopy. No isocyanate bands (2260 cm⁻¹) were found in the infrared spectrum of the reaction mixture. -1 This confirms the completion of the reaction. In this infrared spectrum, at 1749 cm⁻¹... -1 The characteristic signal of the carbonyl group of oxazolidinone was observed at the site.

[0084] Example 3: In a direct reaction procedure, using TBD (C-) at an isocyanate group / hydroxyl molar ratio of 1:2.2. I) as compound (C) and solvent cyclohexanone (DI), using MDI 44 as compound (AI) and glyceryl carbonate as compound Synthesis of hydroxyl-terminated polyoxazolidinone compositions by compound (BI) Glyceryl carbonate (154.03 g, 1.30 mol) (BI) was loaded into the reactor as described above. Cyclohexanone (83 mL) (DI) was then added, and the mixture was stirred (200–300 rpm) and purged with a constant stream of nitrogen throughout the reaction. The reaction mixture was heated to 130 °C. MDI 44 (150.16 g, 0.60 mol) (AI) was dissolved in cyclohexanone (131 mL) and added continuously over a 60-minute time interval using a syringe pump, flushing the pump with acetone (10 mL) after each monomer addition. The reaction was then stirred at 130 °C for an additional 60 minutes. After 60 minutes, TBD (0.83 g, 6.00 mmol) (CI) was added to the reaction mixture, and the reaction was stirred at 130 °C for 120 minutes. The reaction mixture was cooled to 90 °C, and distilled water (150 mL) was added to remove the catalyst. After separating the organic and aqueous layers, the solvent was removed from the organic layer by distillation under vacuum at 140–150 °C. The hot product was then discharged and dried under vacuum at 130 °C for 12 hours. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate).

[0085] During the reaction, a sample of the reaction mixture was extracted and analyzed by infrared spectroscopy. No isocyanate bands (2260 cm⁻¹) were found in the infrared spectrum of the reaction mixture. -1 This confirms the completion of the reaction. In this infrared spectrum, at 1749 cm⁻¹... -1 The characteristic signal of the carbonyl group of oxazolidinone was observed at the site.

[0086] Table: Comparison of results from Examples 1 to 3: (comp.) For comparison, a) data are from Endo et al., Tetrahedron Letters, 2021, Vol. 72, 153086 Scheme 2: 4j, and sections 4-3 and 4-4 in the supporting information.

Claims

1. A method for producing a hydroxyl-terminated oxazolidinone composition, comprising reacting a polyisocyanate compound (A) having two or more isocyanate groups with a compound (B) and optionally in a solvent (D); The compound (B) is glyceryl carbonate. The molar ratio of the isocyanate groups of said compound (B) to those of said polyisocyanate compound (A) is at least 1.5:1, and The method includes a step in which a catalyst (C) is present.

2. The method according to claim 1, wherein the molar ratio of the isocyanate groups of the compound (B) to the polyisocyanate compound (A) is 1.5:1 to 7.0:1, preferably 1.8:1 to 6.0:1, more preferably 1.9:1 to 5.5:1, and most preferably 2.0:1 to 5.0:

1.

3. The method according to claim 1 or 2, wherein the catalyst (C) is present in a molar amount of 0.001 to 2.0 mol% based on the polyisocyanate compound (A), preferably 0.01 to ≤ 1.5 mol%, more preferably ≥ 0.05 to ≤ 1.3 mol%.

4. The method according to any one of claims 1 to 3, wherein the catalyst (C) is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,4-diazabicyclo[2.2.2]octane, imidazole, 1-methylimidazolium, 2-methylimidazolium, 4(5)-methylimidazolium, 2,4(5)dimethylimidazolium, 1-ethylimidazolium, 2-ethylimidazolium, 1-phenylimidazolium, 2-phenylimidazolium, 4(5)phenylimidazolium, N,N -Dimethylaminopyridine, guanidine, 1,1,3,3,-tetramethylguanidine, pyridine, 1-Azanaphthaline, N-methylpiperidine, N-methylmorpholine, N,N'-dimethylpiperazine, N,N-dimethylaniline, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)chloroimine, Tetraphenylphosphonium nitrate and tetraphenylphosphonium carbonate, preferably at least one compound of 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, 1,1,3,3,-tetramethylguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene, more preferably at least one compound of 1,1,3,3,-tetramethylguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

5. The method according to any one of claims 1 to 4, further comprising: a) Polyisocyanate compound (A) and compound (B) are mixed and reacted at a reaction temperature T1, optionally in solvent (D), to form an intermediate (F) containing urethane groups. b) In the presence of catalyst (C) at a reaction temperature T2, the intermediate (F) containing a carbamate group is decarboxylated to form a hydroxyl-terminated oxazolidinone composition.

6. The method according to claim 5, wherein T1 = T2 or T1 < T2.

7. The method according to claim 5 or 6, wherein T2 in step b) is ≥ 80°C to ≤ 290°C, preferably ≥ 90°C to ≤ 180°C, more preferably ≥ 100°C to ≤ 160°C.

8. The method according to any one of claims 5 to 7, wherein T1 < T2 and the catalyst (C) is present in step a).

9. The method according to any one of claims 5 to 7, wherein T1 = T2 and the catalyst (C) is present in step a).

10. The method according to any one of claims 5 to 9, wherein the reaction time t2 in step b) is 10 minutes to 8 hours, preferably 1 hour to 6 hours, more preferably 2 hours to 4 hours.

11. A hydroxyl-terminated oxazolidinone composition available according to any one of claims 1 to 10.

12. The hydroxyl-terminated oxazolidinone composition according to claim 11, wherein the molar ratio of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer is > 0.0:1 to ≤ 100.0:1, preferably ≥ 0.1 to ≤ 20.0:1, more preferably ≥ 0.2:1 to ≤ 5.0:

1.

13. A method for producing hydroxyl-terminated oxazolidinones, wherein a solvent (D) and / or compound (B) are removed from the hydroxyl-terminated oxazolidinone composition obtained according to any one of claims 1 to 10 or the hydroxyl-terminated oxazolidinone composition according to claim 11 or 12.

14. A hydroxyl-terminated oxazolidinone available according to claim 13.

15. The hydroxyl-terminated oxazolidinone according to claim 14, wherein the molar ratio of the 4-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer to the 5-hydroxymethyl-substituted 1,3-oxazolidin-2-one regioisomer is > 0.0:1 to ≤ 100.0:1, preferably ≥ 0.1 to ≤ 20.0:1, more preferably ≥ 0.2:1 to ≤ 5.0:1.

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