EP4731688A1 - Method for the production of a hydroxyl-group terminated oxazolidinone composition - Google Patents

Method for the production of a hydroxyl-group terminated oxazolidinone composition

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Publication number
EP4731688A1
EP4731688A1 EP24732338.9A EP24732338A EP4731688A1 EP 4731688 A1 EP4731688 A1 EP 4731688A1 EP 24732338 A EP24732338 A EP 24732338A EP 4731688 A1 EP4731688 A1 EP 4731688A1
Authority
EP
European Patent Office
Prior art keywords
compound
hydroxyl
carbonate
group terminated
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24732338.9A
Other languages
German (de)
French (fr)
Inventor
Irene Cristina Latorre Martinez
Alan Ekin
Christoph Guertler
Aurel Wolf
Stefan WESTHUES
Sohajl MOVAHHED
Sivathmeehan YOGENDRA
Dean Webster
Jingbo Wu
Eyleen BECKER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Covestro LLC
North Dakota State University Research Foundation
Original Assignee
Covestro Deutschland AG
Covestro LLC
North Dakota State University Research Foundation
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Filing date
Publication date
Application filed by Covestro Deutschland AG, Covestro LLC, North Dakota State University Research Foundation filed Critical Covestro Deutschland AG
Publication of EP4731688A1 publication Critical patent/EP4731688A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention is related to a process for producing a hydroxyl-group terminated oxazolidinone composition comprising the reaction of a polyisocyanate compound with two or more isocyanate groups with glycerol carbonate and optionally in a solvent, wherein the molar ratio of the compound (B) to the isocyanate groups of the 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 is also related to the resulting hydroxyl-group terminated oxazolidinone and a process for producing a hydroxyl-group terminated oxazolidinone by removal of a solvent and/or unreacted glycerol carbonate.

Description

Method for the production of a hydroxyl-group terminated oxazolidinone composition
The invention is related to a process for producing a hydroxyl-group terminated oxazolidinone composition comprising the reaction of a polyisocyanate compound with two or more isocyanate groups with glycerol carbonate and optionally in a solvent, wherein the molar ratio of the compound (B) to the isocyanate groups of the 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 is also related to the resulting hydroxyl-group terminated oxazolidinone and a process for producing a hydroxyl-group terminated oxazolidinone by removal of a solvent and/or unreacted glycerol carbonate.
In Endo et al. (Tetrahedron Letters, 2021, Vol. 72, 153086) the synthesis of 4-hydroxylmethyl 2 - oxazolidinones from glycidyl carbamate derivates catalyzed by bicyclic guanidines are disclosed. In the first step, glycidol and various monoisocyanates (e.g. phenylisocyanate), diisocyanates (e.g. 2,4- diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane) and triisocyanates are reacted to the glycidyl carbamate intermediate, followed by the intramolecular cyclization of the latter carbamate in the presence l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyst in acetone to the 4- hydroxylmethyl 2 -oxazolidinones. All products are 4-hydroxylmethyl 2 -oxazolidinones with 100 % of the 4-hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer. In addition, only moderate yields of the 4-hydroxylmethyl 2 -oxazolidinones results for di- or triisocyanates, although long reaction times and high catalyst loadings are applied.
Objective of the present invention was to identify a simple process for the preparation of a hydroxylgroup terminated oxazolidinone composition and a hydroxyl-group terminated oxazolidinone, wherein the regioselectivity of 4-hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer (4- Oxa) to the 5 -hydroxymethyl substituted l,3-oxazolidm-2-one regioisomer (5-Oxa) can be modified. By adjusting the selectivity of 5-0xa to 4-Oxa, also the melting point of the resulting purified hydroxyl-group terminated oxazolidinone should be controlled, preferably increased. In particular, less toxic and less thermal volatile NCO-reactive compounds with higher storage stability and better availability should be used. Furthermore, the yield to hydroxyl-group terminated oxazolidinones based on polyisocyanates should be increased, wherein the reaction time and necessary catalyst amount should be reduced in parallel.
Surprisingly, it has been found that the upon-referred technical problems can be solved by a process for producing a hydroxyl-group terminated oxazolidinone composition comprising the reaction of a polyisocyanate compound (A) with two or more isocyanate groups with a compound (B) and optionally in a solvent (D), wherein the compound (B) is glycerol carbonate, and wherein the molar ratio of the compound (B) to the isocyanate groups of the polyisocyanate compound (A) is at least 1.5: 1, and wherein the process comprises a step in which a catalyst (C) is present. As used herein, the term "oxazolidinone" is meant to denote compounds containing at least one oxazolidinone groups in the molecule.
The term “hydroxyl-group terminated” oxazolidinone is related to oxazolidinone compounds having at least one, preferably at least two, and more preferably two to three terminal hydroxyl groups, and most preferably two hydroxyl groups.
As used herein, the term "oxazolidinone composition" is meant to denote a composition that comprises the hydroxy-group terminated oxazolidinone, unreacted glycerol carbonate, if used in stochiometric excess and the solvent (D), if the solvent (D) is present.
All embodiments of the present invention can be combined unless the logical teaching clearly suggests that the embodiments cannot be combined.
As used herein, the term "polyisocyanate compound" is meant to denote compounds having two or more isocyanate groups.
In an 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).
In an embodiment of the method according to the invention, the polyisocyanate compound (A) is at least one polyisocyanate accessible in various ways, for example by phosgenation in the liquid or gas phase or by a phosgene-free route, for example by thermal urethane cleavage.
In an embodiment of the method according to the invention, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates from the molecular weight range of 140 g/mol to 600 g/mol having aliphatically 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-l,5- diisocyanatopentane, l,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-l,6- diisocyanatohexane, 1,8-diisocyanatooctane, 1,10-diisocyanatodecane, 1,12-diisocyanatododecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and l,4-bis(isocyanatomethyl)cyclohexane, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4’- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-dicyclohexyl propane, 1 -isocyanate- 1 -methyl -4(3)isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbomane, or any polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure, prepared by modification of simple aliphatic diisocyanates, for example those of the type mentioned above, as described for example in J. Prakt. Chem. 336 (1994) 185 - 200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299 or by mixtures of at least two such polyisocyanates, and 1,3- and 1,4- bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and l,4-bis(2-isocyanatopropan-2- yl)benzene (tetramethylxylylene diisocyanate, TMXDI), l,3-bis(isocyanatomethyl)-4- methylbenzene, l,3-bis(isocyanatomethyl)-4-ethylbenzene, l,3-bis(isocyanatomethyl)-5- m ethylbenzene, l,3bis(iscyanatomethyl)-2,4,6-trimethlybenzene, l,3-bis(isocyanatomethyl)-4,5- dimethylbenzene, l,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, l,4-bis(isocyanatomethyl)-
2.3.5.6-tetram ethylbenzene, 1 ,3 -bis(isocyanatomethyl)-5 -tert-butylbenzene, 1,3- bis(isocyanatomethyl)-4-chlorobenzene, l,3-bis(isocyanatomethyl)-4,5-dichlorobenzene, 1,3- bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, l,4-bis(isocyanatomethyl)-2, 3,5,6- tetrachlorobenzene, l,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromobenzene, l,4-bis(2- isocyanatoethyl)benzene and l,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-l,4-diisocyanatobenzene, the isomeric diethylphenylene diisocyanates, diisopropylphenylene diisocyanates, diisododecylphenylene diisocyanates and biphenyl diisocyanates, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2‘-, 2,4'- and 4,4'- diisocyanatodiphenylmethane (MDI), 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'- diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI), diphenylether diisocyanate, ethylene glycol diphenylether diisocyanate, diethylene glycol diphenylether diisocyanate, 1,3- propylene glycol diphenylether diisocyanate, benzophenone diisocyanate, triisocyanatobenzene,
2.4.6-triisocyanatotoluene, trimethylbenzene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3- methyldiphenylmethane-4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-l-[(5- isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane-3,5,2',4',6'- pentaisocyanate, and also the polynuclear homologues of diisocyanatodiphenylmethane known as “polymer-MDI”, and also the polyisocyanates having urethane and/or isocyanurate structures obtainable from monomeric 2,4- and/or 2,6-TDI by reaction with polyols and/or oligomerization, preferably trimerization, which are obtainable by any known methods, described for example 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 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 are mixtures of at least two such polyisocyanates, and also those polyisocynanate compounds bearing both 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.
More preferred, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates from the molecular weight range of 140 g/mol to 600 g/mol having aliphatically and/or aromatically bonded isocyanate groups, examples being 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), l,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4- trimethyl-l,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and l,4-bis(isocyanatomethyl)cyclohexane, l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4’- and 4,4'- diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-dicyclohexyl propane, or any polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure, prepared by modification of simple aliphatic diisocyanates, for example those of the type mentioned above, as described for example in J. Prakt. Chem. 336 (1994) 185 - 200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299, and 1,3- and l,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4- bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 1,3- bis(isocyanatomethyl)-4-methylbenzene, l,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3- bis(isocyanatomethyl)-5-methylbenzene, l,3-bis(iscyanatomethyl)-2,4,6-trimethlybenzene, 1,3- bis(isocyanatomethyl)-4,5-dimethylbenzene, l,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4- bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, l,3-bis(isocyanatomethyl)-5-tert-butylbenzene, l,4-bis(2-isocyanatoethyl)benzene, l,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-l,4-diisocyanatobenzene, diisopropylphenylene diisocyanates, diisododecylphenylene diisocyanates and biphenyl diisocyanates, 3,3’- dimethoxybiphenyl-4,4'-diisocyanate, 2.2'-. 2,4’- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5- diisocyanatonaphthalene (NDI), diphenylether diisocyanate, ethylene glycol diphenylether diisocyanate, 1,3-propylene glycol diphenylether diisocyanate, triisocyanatobenzene, 2,4,6- triisocyanatotoluene, trimethylbenzene triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-l-[(5-isocyanato-2-methylphenyl)methyl]benzene and also the polynuclear homologues of diisocyanatodiphenylmethane known as “polymer-MDI”, and also the polyisocyanates having urethane and/or isocyanurate structures obtainable from monomeric 2,4- and/or 2,6-TDI by reaction with polyols and/or oligomerization, preferably trimerization, which are obtainable by any known methods, described for example 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 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, and also those polyisocyanate compounds bearing both 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.
And most preferred, the polyisocyanate compound (A) is at least one compound selected from the group consisting of polyisocyanates from the molecular weight range of 140 g/mol to 600 g/mol having aliphatically and/or aromatically bonded isocyanate groups, examples being 1,5- diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), l-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 l,4-bis(2-isocyanatopropan-2- yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 2,2‘-, 2,4'- and 4,4'- diisocyanatodiphenylmethane (MDI), 3, 3 '-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'- diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI).
A mixture of two or more of the aforementioned polyisocyanate compounds (A) can also be used. As used herein, the term "aliphatic polyisocyanate compound" is meant to denote compounds having two or more isocyanate groups and aliphatic moieties and can contain aromatic moieties. The aliphatic polyisocyanate compound means an linear aliphatic or a cycloaliphatic polyisocyanate compound. Within the aliphatic polyisocyanate compound the isocyanate moiety is not directly bound to the aromatic moiety. Xylylene diisocyanate (XDI) is an example of an aliphatic polyisocyanate with isocyanate moieties which are not directly bound to the aromatic moiety, wherein the isocyanate group is bound through a methylene group to the phenyl group. In a preferred embodiment of the method according to the invention the polyisocyanate compound (A) is an aliphatic (A-l).
In an embodiment of the method according to the invention, the aliphatic polyisocyanate compound (A-l) is at least one compound selected from the group consisting of polyisocyanates from the molecular weight range of 140 g/mol to 400 g/mol having aliphatically bonded isocyanate groups, examples being 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 2-methyl-l,5- diisocyanatopentane, l,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 l,4-bis(isocyanatomethyl)cyclohexane, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4’- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-2,2-dicyclohexyl propane, 1 -isocyanate- 1 -methyl -4(3)isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbomane, 1,3- and l,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and l,4-bis(2- isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), 1,3- bis(isocyanatomethyl)-4-methylbenzene, l,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3- bis(isocyanatomethyl)-5-methylbenzene, l,3bis(iscyanatomethyl)-2,4,6-trimethlybenzene, 1,3- bis(isocyanatomethyl)-4,5-dimethylbenzene, l,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4- bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, l,3-bis(isocyanatomethyl)-5-tert-butylbenzene,
1.3-bis(isocyanatomethyl)-4-chlorobenzene, l,3-bis(isocyanatomethyl)-4,5-dichlorobenzene, 1,3- bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, l,4-bis(isocyanatomethyl)-2, 3,5,6- tetrachlorobenzene, l,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromobenzene, l,4-bis(2- isocyanatoethyl)benzene and l,4-bis(isocyanatomethyl)naphthalene, or any polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure, prepared by modification of simple aliphatic diisocyanates, for example those of the type mentioned above, as described for example in J. Prakt. Chem. 336 (1994) 185 - 200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP -A 0 336 205, EP -A 0 339 396 and EP -A 0 798 299 or by mixtures of at least two such polyisocyanates.
More preferred, the aliphatic polyisocyanate compound (A-l) is at least one compound selected from the group consisting of polyisocyanates from the molecular weight range of 140 g/mol to 400 g/mol having aliphatically bonded isocyanate groups, examples being 1,4-diisocyanatobutane, 1,5- diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), l,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-l,6- diisocyanatohexane, 1,8-diisocyanatooctane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4- bis(isocyanatomethyl)cyclohexane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4’- and 4,4'-diisocyanatodicyclohexylmethane (EI12-MDI), 4,4'- diisocyanato-2,2-dicyclohexyl propane, 1,3- and l,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and l,4-bis(2-isocyanatopropan-2-yl)benzene (tetramethylxylylene diisocyanate, TMXDI), l,3-bis(isocyanatomethyl)-4-methylbenzene, l,3-bis(isocyanatomethyl)-4- ethylbenzene, l,3-bis(isocyanatomethyl)-5-methylbenzene, l,3bis(iscyanatomethyl)-2,4,6- trimethlybenzene, l,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, l,4-bis(isocyanatomethyl)-2,5- dimethylbenzene, l,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3- bis(isocyanatomethyl)-5-tert-butylbenzene, l,3-bis(isocyanatomethyl)-4-chlorobenzene, 1,3- bis(isocyanatomethyl)-4,5-dichlorobenzene, l,3-bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, l,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, l,4-bis(isocyanatomethyl)-2, 3,5,6- tetrabromobenzene, l,4-bis(2-isocyanatoethyl)benzene and l,4-bis(isocyanatomethyl)naphthalene, or any polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetnone structure, prepared by modification of simple aliphatic diisocyanates, for example those of the type mentioned above, as described for example in J. Prakt. Chem. 336 (1994) 185 - 200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP-A 0 336 205, EP-A 0 339 396 and EP-A 0 798 299 or by mixtures of at least two such polyisocyanates.
And most preferred, the aliphatic polyisocyanate compound (A-l) is one or more compound(s) and selected from the group consisting of 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI),
1.6-diisocyanatohexane (hexamethylene diisocyanate, HDI), and l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI).
A mixture of two or more of the aforementioned aliphatic polyisocyanate compound (A-l) can also be used
As used herein, the term "aromatic polyisocyanate compound" is meant to denote compounds having two or more isocyanate groups and must contain aromatic and can additionally contain aliphatic moieties. Thereby, the term "aromatic polyisocyanate compound" is meant to denote compounds bearing two or more isocyanate groups which are directly bound to the aromatic moiety e.g. 2,4- and
2.6-diisocyanatotoluene (toluene diisocyanate, TDI) or 2,2‘-, 2,4'- and 4,4'- diisocyanatodiphenylmethane (MDI). In a less preferred embodiment of the method according to the invention the polyisocyanate compound (A) is an aromatic polyisocyanate compound (A-2).
In a preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound and is selected from the group consisting of aromatic diisocyanates and triisocyanate are of the molecular weight range from 160 g/mol to 600 g/mol, such as 1,2-, 1,3- and 1,4-diisocyanatobenzene (phenylene diisocyanate), 2,4- and 2,6- diisocyanatotoluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-l,4-diisocyanatobenzene, diisopropylphenylene diisocyanates, diisododecylphenylene diisocyanates and biphenyl diisocyanates, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2‘-, 2,4'- and 4,4'- diisocyanatodiphenylmethane (MDI), 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'- diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI), diphenylether diisocyanate, ethylene glycol diphenylether diisocyanate, 1,3-propylene glycol diphenylether diisocyanate, triisocyanatobenzene, 2,4,6-triisocyanatotoluene, trimethylbenzene triisocyanate, 3- methyldiphenylmethane-4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-l-[(5- isocyanato-2-methylphenyl)methyl]benzene and also the polynuclear homologues of diisocyanatodiphenylmethane known as “polymer-MDI”, and also the polyisocyanates having urethane and/or isocyanurate structures obtainable from monomeric 2,4- and/or 2,6-TDI by reaction with polyols and/or oligomerization, preferably trimerization, which are obtainable by any known methods, described for example 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 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.
In a more preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound and is selected from the group consisting of aromatic diisocyanates and triisocyanates of the molecular weight range from 160 g/mol to 600 g/mol, such as 1,2-, 1,3- and 1,4-diisocyanatobenzene (phenylene diisocyanate), 2,4- and 2,6- diisocyanatotoluene (toluene diisocyanate, TDI), 2,3,5,6-tetramethyl-l,4-diisocyanatobenzene, the isomeric diethylphenylene diisocyanates, diisopropylphenylene diisocyanates, diisododecylphenylene diisocyanates and biphenyl diisocyanates, 3, 3 '-dimethoxybiphenyl -4,4'- diisocyanate, 2.2’-. 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI), diphenylether diisocyanate, ethylene glycol diphenylether diisocyanate, diethylene glycol diphenylether diisocyanate, 1,3-propylene glycol diphenylether diisocyanate, benzophenone diisocyanate, triisocyanatobenzene, 2,4,6-triisocyanatotoluene, trimethylbenzene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-l-[(5-isocyanato-2-methylphenyl)methyl]benzene, 4-methyl-diphenylmethane- 3,5,2',4',6'-pentaisocyanate, and also the polynuclear homologues of diisocyanatodiphenylmethane known as “polymer-MDI”, and also the polyisocyanates having urethane and/or isocyanurate structures obtainable from monomeric 2,4- and/or 2,6-TDI by reaction with polyols and/or oligomerization, preferably trimerization, which are obtainable by any known methods, described for example 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 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 are mixtures of at least two such polyisocyanates.
In an even more preferred embodiment of the method according to the invention, the aromatic polyisocyanate compound (A-2) is at least one compound and is selected from the group consisting of 2,2‘-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyl diphenylmethane-4,4'- diisocyanate, 4,4'-diisocyanatodiphenylethane, 1,5-diisocyanatonaphthalene (NDI) and 2,4-, and 2,6-diisocyanatetoluene (TDI).
And most preferred, the aromatic polyisocyanate compound (A-2) is at least one compound selected from the group consisting of 2,2‘-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane and 4,4'-diisocyanatodiphenylmethane.
A mixture of two or more of the aromatic polyisocyanate compounds (A-2) can also be used. Glycerol carbonate is the compound (B) according to the invention.
In a preferred embodiment of the invention, the molar ratio of the compound (B) to the isocyanate groups of the polyisocyanate compound (A) is from 1.5:1 to 7.0: 1, preferably from 1.8: 1 to 6.0: 1 more preferably from 1.9: 1 to 5.5: 1, and most preferably from 2.0: 1 to 5.0:1. If the molar ratio of the compound (B) to the isocyanate groups of the polyisocyanate compound (A) is lower than 1.5: 1 the viscosity of the resulting hydroxyl-group terminated oxazolidinone composition comprising the hydroxyl-group terminated oxazolidinone significantly increases, If the molar ratio is higher than 7.0: 1 higher amounts of glycerol carbonate need to be removed.
In an embodiment of the method according to the invention, the catalyst (C) is present in a molar amount of 0.001 to 2.0 mol-%, preferably of 0.001 to 2.0 mol-%, preferably of 0.01 to < 1.5 mol-%, more preferred > 0.05 to < 1.3 mol-%, based on the polyisocyanate compound (A). If catalyst amounts below 0.001 mol.-% are used, the conversion decreases and catalyst amounts higher than 2.0 mol-% causes the formation of side products.
In a preferred embodiment of the invention the catalyst (C) is a Lewis- and/or Bronsted base such as substituted or non-substituted ammonium halide, a substituted or non-substituted phosphonium halide, an amine, a metal hydroxide, a metal carbonate, a metal alkoxide, a metal acetate, a metal formiate, a metal molybdate, a metal vanadate and/or a metal phosphate
In a more preferred embodiment of the invention the catalyst (C) is at least one compound selected from the group consisting of is at least one compound selected from the group consisting of , 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU), l,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), 1,4- Diazabicyclo[2.2.2]octane (DABCO), Imidazole, 1 -Methylimidazole, 2-Methylimidazole, 4(5)- Methylimidazole, 2,4(5)Dimethylimidazole, 1 -Ethylimidazole, 2-Ethylimidazole, 1- Phenylimidazole, 2-Phenylimidazole, 4(5)Phenylimidazole, AA'-dimcthylaminopyridinc. Guanidine, 1,1, 3, 3, -Tetramethylguanidine (TMG), Pyridine, 1 -Azanaphthaline (Chinolin), N- Methylpiperidine, A-Methylmorpholine, A,A‘-Dimethylpiperazine, A,jV-Dimethylaniline, lithium carbonate, sodium carbonate, potassium carbonate, caesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)iminium chloride, 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 l,5,7-Triazabicyclo[4.4.0]dec-5-ene, more preferably 1,1, 3, 3, -Tetramethylguanidine , and 1,5,7- Triazabicyclo [4.4.0] dec-5 -ene .
The use of l,8-Diazabicyclo[5.4.0]undec-7-ene, 1,4-Diazabicyclo[2.2.2]octane, 1, 1,3,3, - Tetramethylguanidine, and l,5,7-Triazabicyclo[4.4.0]dec-5-ene, preferably 1, 1,3,3, -
Tetramethylguanidin , and l,5,7-Triazabicyclo[4.4.0]dec-5-en as catalyst (C) leads to an improved reactivity in the reaction process with higher conversion rates.
In an embodiment of the reaction is in the solvent (D).
In an embodiment of the invention the calculated mass ratio of the sum of diisocyanate compound (A), the compound (B), and catalyst (C) with respect to the sum of diisocyanate compound (A), the compound (B), the catalyst (C), and the solvent (D) ranges from 40 wt-% to 100 wt-%, preferred from 50 wt-% to 90 wt-% and more preferred from 60 wt-% to 80 wt-%.
The solvent (D) is defined in alignment to the general definition as a substance that dissolves a solute, i.e. compound (A) and/or compound (B) and/or compound (C) but does not (chemically) react with compound (A), compound (B) and/or the catalyst (C), in particular the polyisocyanate compound (A).
Suitable solvents (D) according to the invention are solvents with a boiling point equal or lower than 200 °C, preferably equal or lower than 190 °C and more preferably equal or lower than 180 °C at 1 bar (absolute).
In a preferred embodiment of the invention the reaction is in the presence of a solvent (D), wherein the solvent (D) is one or more compounds and is selected from the group consisting of chlorobenzene, the different isomers of dichlorobenzene, dimethylformamide, A,A-dimethylacetamide, tetrahydrofuran, acetone, methyl ethyl ketone, 1,2-Dimethoxyethane, l-Methoxy-2-(2- m ethoxy ethoxy)ethane, cyclohexanone, benzonitrile, methyl isobutyl ketone, and different isomers of dioxane preferably acetone, cyclohexanone, benzonitrile, methyl isobutyl ketone.
The reaction according to the invention is performed in the absence of a solvent (E) with a boiling point higher than 200 °C, preferably higher than 190 °C and more preferably higher than 180 °C at 1 bar (absolute).
Such solvents (E) include for example cyclic carbonate, such as ethylencarbonate or propylencarbonate, A-methylpyrrolidone (NMP) and sulfolane. The absence of this additional solvent (E) reduces the energy-intensive and time-consuming removal process, e.g. distillation, of this high boiling solvents.
In the absence of an additional solvent (E) means solvent amounts of (E) of less than 5 wt-% preferably 4 wt-% more preferably 2 wt-%.
In an embodiment of the invention the reaction temperature of the one-step process is of > 20 °C to < 180 °C, preferably of > 40 °C to < 160 °C, and more preferably of > 60 °C to < 140 °C.
In an embodiment of the invention the reaction time of the one-step process is of 10 min to 8 h, preferably of 1 h to 6 h, and more preferably of 2 h to 4 h.
In an embodiment of the invention the process further comprising: a) Mixing and reacting the polyisocyanate compound (A) and the compound (B), and optionally in the solvent (D) at a reaction temperature T1 forming a carbamate group containing intermediate (F), b) Decarboxylating the carbamate group containing intermediate (F) in the presence of the catalyst (C) at a reaction temperature T2 forming the hydroxyl-group terminated oxazolidinone composition.
In a less-preferred embodiment of the invention the process step a) comprises: a-1) Mixing the polyisocyanate compound (A) and the compound (B), optionally the catalyst (C), and optionally the solvent (D) to provide a mixture (G), a-2) Reacting the mixture (G) at the reaction temperature T1 forming the carbamate group containing intermediate (F).
In an alternative, less-preferred embodiment of the invention the process step a comprises: a-i) Mixing the polyisocyanate compound (A), optionally the catalyst (C), and optionally the solvent (D) to provide a mixture (H), a-ii) Adding the compound (B) at the reaction temperature T1 to the mixture (H) and forming the carbamate group containing intermediate (F).
In a further alternative, preferred embodiment of the invention the process step a comprises: a-I.) Mixing the compound (B), optionally the catalyst (C) and optionally the solvent (D) to provide a mixture (I), a-II.) Adding the polyisocyanate compound (A) at the reaction temperature T1 to the mixture (I) and forming the carbamate group containing intermediate (F).
Due to plant safety considerations, the latter addition of the polyisocyanate compound (A) to the mixture (I) in step a-II.) is preferable. In an embodiment of the invention the process the reaction temperature T1 in step a) is equal to the reaction temperature T2 in step b) (T1 = T2) or reaction temperature T1 in step a) is lower than the reaction temperature T2 in step b) (T1 < T2).
In an embodiment of the invention T2 in step b) is of > 80 °C to < 290 °C, preferably of > 90 °C to < 180 °C, and more preferably of > 100 °C to < 160 °C.
In a first preferred embodiment (1) of the invention the process further comprising: a) Mixing and reacting the polyisocyanate compound (A) and the compound (B), the catalyst (C) and optionally in the solvent (D) at a reaction temperature Tl forming a cyclic carbonate group comprising a carbamate group containing intermediate (F), b) Decarboxylating the carbamate group containing intermediate (F) in the presence of the catalyst (C) at a reaction temperature T2 forming the hydroxyl-group terminated oxazolidinone composition, wherein T1 < T2.
In a preferred embodiment within the first preferred embodiment ( 1) of the invention T1 in step a) is of > 20 °C to < 180 °C, preferably of > 20 °C to < 130 °C, and more preferably of > 20 °C to < 60 °C. In a preferred embodiment of the invention T2 in step b) is of > 80 °C to < 290 °C, preferably of > 90 °C to < 180 °C, and more preferably of > 100 °C to < 160 °C. If T2 in step b) is above 290 °C an increased decomposition rate of the hydroxyl-group terminated oxazolidinone composition is observed. If T2 is below 80 °C, the decarboxylation reaction rate decreases resulting in reduced conversion rates.
In a preferred embodiment within the first preferred embodiment (1) of the invention step a) is in the presence of the solvent (D) in particular, if an aromatic polyisocyanate compound (A-2) is used forming a solid carbamate group containing intermediate (F) at reaction temperature.
In an alternative, preferred embodiment within the first preferred embodiment (1) of the invention, step a) is in the absence of the solvent (D) wherein the avoidance of solvent (D) is preferably used for aliphatic polyisocyanate compounds (A-2) like HDI and IPDI, wherein the aliphatic polyisocyanate compound (A-l) forming processable, liquid, stirrable carbamate group containing intermediate (F) at reaction temperature.
In a preferred embodiment within the first preferred embodiment (1) of the invention the reaction time tl in step a) is of 10 min to 8 h, preferably of 1 h to 7 h, and more preferably of 2 h to 6 h. If the reaction time tl is less than 10 min, the conversion into the carbamate group containing intermediate (F) is decreasing, wherein to long reaction time higher than 8 h increase the formation of oligomeric products of side and/or subsequent reactions.
In a preferred embodiment within the first preferred embodiment (1) of the invention the reaction time t2 in step b) is of 10 min to 8 h, preferably of 1 h to 6 h, and more preferably of 2 h to 4 h. If the reaction time t2 is less than 10 min, the conversion into the hydroxyl -group terminated oxazolidinone composition is decreasing, wherein to long reaction time higher than 8 h increase the formation of oligomeric products of side and/or subsequent reactions.
In a second preferred embodiment (2) of the invention the process further comprising: a) Mixing and reacting the polyisocyanate compound (A) and the compound (B), in the absence of the catalyst (C) and optionally in the solvent (D) at a reaction temperature T1 forming a cyclic carbonate group comprising a carbamate group containing intermediate (F), b) Decarboxylating the carbamate group containing intermediate (F) in the presence of the catalyst (C) at a reaction temperature T2 forming the hydroxyl-group terminated oxazolidinone composition, wherein T1 = T2.
In a preferred embodiment within the second preferred embodiment (2) of the invention T1 in step a) and T2 in step b) is of > 80 °C to < 290 °C, preferably of > 90 °C to < 180 °C, and more preferably of > 100 °C to < 160 °C. If T2 in step b) is above 290 °C an increased decomposition rate of the hydroxyl-group terminated oxazolidinone composition is observed. If T2 is below 80 °C, the decarboxylation reaction rate decreases resulting in reduced conversion rates.
In a preferred embodiment within the second preferred embodiment (t2) of the invention step a) is in the presence of the solvent (D) in particular, if an aromatic polyisocyanate compound (A-2) is used forming a solid carbamate group containing intermediate (F) at reaction temperature.
In an alternative, preferred embodiment within the second preferred embodiment (2) of the invention, step a) is in the absence of the solvent (D) wherein the avoidance of solvent (D) is preferably used for aliphatic polyisocyanate compounds (A-2) like HDI and IPDI, wherein the aliphatic polyisocyanate compound (A-l) forming processable, liquid, stirrable carbamate group containing intermediate (F) at reaction temperature.
In a preferred embodiment within the second preferred embodiment (2) of the invention the reaction time tl in step a) is of 10 min to 8 h, preferably of 1 h to 7 h, and more preferably of 2 h to 6 h. If the reaction time tl is less than 10 min, the conversion into the carbamate group containing intermediate (F) is decreasing, wherein to long reaction time higher than 8 h increase the formation of oligomeric products of side and/or subsequent reactions. The reaction time is defined according to the invention as sum of the addition time of at least one reactant and the subsequent reaction time, wherein the reaction mixture is stirred and reacted.
In a preferred embodiment within the second preferred embodiment (2) of the invention the reaction time t2 in step b) is of 10 min to 8 h, preferably of 1 h to 6 h, and more preferably of 2 h to 4 h . If the reaction time t2 is less than 10 min, the conversion into the hydroxyl -group terminated oxazolidinone composition is decreasing, wherein to long reaction time higher than 8 h increase the formation of oligomeric products of side and/or subsequent reactions. Another subject matter of the invention is a hydroxyl -group terminated oxazolidinone composition obtainable according to the process according to the invention.
In an embodiment of the invention the molar ratio of the 4-hydroxymethyl substituted 1,3-oxazolidin- 2-one regioisomer to the 5 -hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer of the hydroxyl-group terminated oxazolidinone composition is of > 0,0 to 1 to <100,0 to 1, preferred > 0,1 to <20,0 to 1 and more preferred > 0,2 to 1 to <5,0 to 1, wherein the molar ratio of the 4- hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer to the 5 -hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer is estimated according to the NMR measurement method disclosed within the experimental section.
Another subject matter of the invention is a process for producing a hydroxyl-group terminated oxazolidinone, wherein the solvent (D) and/or compound (B) is removed from the hydroxyl-group terminated oxazolidinone composition obtained according to the process to the invention or the hydroxyl-group terminated oxazolidinone composition obtainable according to the process according to the invention. The removal of the solvent (D) and/or glycerol carbonate as unreacted compound (B) can be beneficial for future polymerization applications since e.g. halogen containing solvents and/or the unreacted glycerol carbonate might disturb these polymerization reactions and negatively impact the resulting polymerization products.
In an embodiment of the invention the non-reacted compound (B) and/or the solvent (D) is removed by a thermal treatment method, preferably by distillation and/or by extraction, more preferably by thin-film evaporation.
Another subject matter of the invention is a hydroxyl-group terminated oxazolidinone obtainable according to the process to the invention.
In an embodiment of the invention the molar ratio of the 4-hydroxymethyl substituted 1,3-oxazolidin- 2-one regioisomer to the 5 -hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer of the hydroxyl-group terminated oxazolidinone is of > 0,0 to 1 to <100,0 to 1, preferred > 0,1 to <20,0 to 1 and more preferred > 0,2 to 1 to <5,0 to 1, wherein the molar ratio of the 4-hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer to the 5 -hydroxymethyl substituted l,3-oxazolidin-2- one regioisomer is estimated by to the NMR measurement method disclosed within the experimental section. Examples
The present invention will be further described with reference to the following examples without wishing to be limited by them.
Compound (A)
A-I: MDI, Methylene diphenyl diisocyanate (MDI 44), purity >99 %, Covestro AG,
Germany.
Compound (B)
For the calculation of the experimental molar ratios, a compound purity of 100 % was assumed for the compound. Possible impurities e.g., alcoholic compounds were neglected for the calculations.
B-I: Glycidol, for details see literature Endo et al.
B-II: Glycerol carbonate, purity >95 %, UBE Corporation Europe, Spain.
Catalyst (C)
C-I: Triazabicyclodecene (TBD), punty 98 %, Sigma Aldrich.
The concentration of catalyst is given in ppm related to the theoretical mass of the employed monomers.
Solvent (D)
D-I: Acetone, purity >99 %, Fisher Scientific.
D-II: Dichloromethane, for details see literature Endo et al.
All Chemicals were used as received without further purification.
Characterization of oxazolidinone
NMR
NMR measurements were recorded using a Bruker AV III 600 NMR instrument: H: 80 MHz or 400 MHz at 293 K. The spectra were calibrated to the respective solvent peak: 1 H: 2.50 ppm (DMSO-de). The chemical shift (5) was expressed in ppm. The evaluation of the NMR spectra was performed by using MestReNova from Mestrelab Research, S.L. The isomer ratio between 4-0xa and 5 -Oxa was determined by integrating the signal of the protons of the methylene bridge between the aromatic rings of both isomers in comparison. DSC
The thermal properties of the oxazolidinones were characterized by dual scanning calorimetry (DSC) The measurements were performed on a Mettler Toledo DSC 3+/500. The sample (6 to 15 mg) was weighed in a 40 pL Alox pan with lid, heated from -40 °C to 170 °C with a heating rate of 10 K/min under argon flow (80 mL/min) in three cycles with holding phases of 10 min each. The second heating cycle was used for the evaluation of the melting point (Tm). For the melting point the peak minimum was determined. For data analysis the software STAR6 SW 16.30 was used.
Reactor
The reaction was performed in a 4 neck round bottom flask (500 m ), equipped with a glass reflux condenser, a gas inlet (N2), a syringe pump (IP-SYRDOS2-HP-XLP from SyrDos), a glass inlet tube equipped with a temperature probe (GFX 460 from Ebro) and an overhead KPG agitator (RW20 from IKA). The round bottom flask was heated with a heating mantle from Winkler (WM/BRI/250 with a maximum heating capacity of 120 W) which was connected to the temperature probe with an RB 1691 B-S from Ebro.
Example 1 (Comparative): Synthesis ofhydroxyl-terminated oxazolidinone-based composition with MD144 as compound (A-I) and glycidol as compound (B-l) using TBD (C-I) as compound (C) and the solvent dichloromethane (D-II) in a 2-step reaction procedure with molar ratio of isocyanate groups to hydroxyl groups of 1:2.
Synthesis data applied to Endo et al. Tetrahedron Letters, 2021, Vol. 72, 153086, in particular synthesis data disclosed in paragraph 4-3 and 4-4 on page S9 and S10 of supporting information.
Example 2: Synthesis of hydroxyl-terminated oxazolidinone-based composition with MD1 44 as compound (A-I) and glycerol carbonate as compound (B-Il) using TBD (C-I) as compound (C) and the solvent acetone (D-I) in a 2-step reaction procedure with molar ratio of isocyanate groups to hydroxyl groups of 1:2.1.
A reactor as previously described was charged with glycerol carbonate (126.97 g, 1.06 mol) (B-II) and TBD (0.70 g, 5.00 mmol) (C-I). Then acetone (200 mL) (D-I) was added, and the mixture was stirred (200-300 rpm) and flushed with a constant nitrogen flow throughout the reaction. The reaction took place at room temperature. MDI 44 (125.13 g, 0.50 mol) (A-I) was solved in acetone (240 mL) and was added in a continuous manner within a time range of 60 minutes by using the syringe pump and after the addition of the monomer the pump was rinsed with acetone (40 mL). Afterwards the reaction was stirred for further 60 minutes. The solvent was removed in vacuo and the carbamate group containing intermediate product was dried in vacuo at 50 °C for 12 hours.
The dry carbamate group containing intermediate product was added in a clean reaction vessel, stirred (200-300 rpm) and flushed with a constant nitrogen flow throughout the reaction. The reaction took place at 140 °C inside the vessel. The reaction was stirred and heated for further 180 minutes before the hot reaction mixture was drained. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate).
Within the course of the reaction, samples of the reaction mixture were taken and analyzed by IR-spectroscopy. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm 1) in the IR spectrum from the reaction mixture. In the IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1749 cm 1.
Example 3: Synthesis ofhydroxyl-terminated polyoxazolidinone-based composition withMDI 44 as compound (A-I) and glycerol carbonate as compound (B-l) using TBD (C-I) as compound (C) and the solvent cyclohexanone (D-l) in a direct reaction procedure with molar ratio of isocyanate groups to hydroxyl groups of 1:2.2.
A reactor as previously described was charged with glycerol carbonate (154.03 g, 1.30 mol) (B-I). Then cyclohexanone (83 mL) (D-I) was added, and the mixture was stirred (200-300 rpm) and flushed with a constant nitrogen flow throughout the reaction. The reaction mixture was heated up to 130 °C. MDI 44 (150.16 g, 0.60 mol) (A-I) was solved in cyclohexanone (131 mL) and was added in a continuous manner within a time range of 60 minutes by using the syringe pump and after the addition of the monomer the pump was rinsed with acetone (10 mL). Afterwards the reaction was stirred for further 60 minutes at 130 °C. After 60 minutes TBD (0.83 g, 6.00 mmol) (C-I) was added to the reaction mixture and the reaction was stirred for 120 minutes at 130 °C. The reaction mixture was cooled down to 90 °C and distilled water (150 mL) was added to the reaction mixture to remove the catalyst. After the separation of the organic and aqueous layer, the solvent was removed from the organic layer in vacuo via distillation at 140-150 °C and the hot product was drained and dried in vacuo at 130 °C for 12 hours. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate).
Within the course of the reaction, samples of the reaction mixture were taken and analyzed by IR-spectroscopy. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm 1) in the IR spectrum from the reaction mixture. In the IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1749 cm'1.
Table: Comparison of the results of Examples 1 to 3:
(comp.) comparative, a) data from Endo et al. Tetrahedron Letters, 2021, Vol. 72, 153086 Scheme 2: 4j, and chapter 4-3 and 4-4 in supporting information.

Claims

Claims:
1. A process for producing a hydroxyl-group terminated oxazolidmone composition comprising the reaction of a polyisocyanate compound (A) with two or more isocyanate groups with a compound (B) and optionally in a solvent (D); wherein the compound (B) is glycerol carbonate, wherein the molar ratio of the compound (B) to the isocyanate groups of the polyisocyanate compound (A) is at least 1.5: 1, and wherein the process comprises a step in which a catalyst (C) is present.
2. The process according to claim 1, wherein the molar ratio of the compound (B) to the isocyanate groups of the polyisocyanate compound (A) is from 1.5: 1 to 7.0: 1, preferably from 1.8: 1 to 6.0: 1 more preferably from 1.9: 1 to 5.5: 1, and most preferably from 2.0: 1 to 5.0: 1.
3. The process according to claim 1 or 2, wherein the catalyst (C) is present in a molar amount of 0.001 to 2.0 mol-%, preferably of 0.01 to < 1.5 mol-%, more preferred > 0.05 to < 1.3 mol-%, based on the polyisocyanate compound (A).
4. The process according to any one of claims 1 to 3, wherein the catalyst (C) is at least one compound selected from the group consisting of , l,8-Diazabicyclo[5.4.0]undec-7-ene, l,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1,4-Diazabicyclo[2.2.2]octane, Imidazole, 1- Methylimidazole, 2-Methylimidazole, 4(5)-Methylimidazole, 2,4(5)Dimethylimidazole, 1- Ethylimidazole, 2-Ethylimidazole, 1 -Phenylimidazole, 2-Phenylimidazole,
4(5)Phenylimidazole, 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, caesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, bis(triphenylphosphine)iminium chloride, tetraphenylphosphonium nitrate, and tetraphenylphosphonium carbonate, preferably l,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 1,1, 3, 3, -Tetramethylguanidine , and 1,5,7- Triazabicyclo [4.4.0] dec-5 -ene .
5. The process according to any one of claims 1 to 4, further comprising: a) Mixing and reacting the polyisocyanate compound (A) and the compound (B), and optionally in the solvent (D) at a reaction temperature T1 forming a carbamate group containing intermediate (F) , b) Decarboxylating the carbamate group containing intermediate (F) in the presence of the catalyst (C) at a reaction temperature T2 forming the hydroxyl-group terminated oxazolidinone composition.
6. The process according to claim 5, wherein T1 = T2 or T1 < T2.
7. The process according to claim 5 or 6, wherein T2 in step b) is of > 80 °C to < 290 °C, preferably of > 90 °C to < 180 °C, and more preferably of > 100 °C to < 160 °C.
8. The process according to any one of claims 5 to 7, wherein T1 < T2 and the catalyst (C) is present in step a).
9. The process according to any one of claims 5 to 7, wherein T1 = T2 and the catalyst (C) is absent in step a).
10. The process according to any one of claims 5 to 9, wherein a reaction time t2 in step b) is of 10 min to 8 h, preferably of 1 h to 6 h, and more preferably of 2 h to 4 h.
11. A hydroxyl -group terminated oxazolidinone composition obtainable according to any one of claims 1 to 10.
12. The hydroxyl-group terminated oxazolidinone composition according to claim 11, wherein the molar ratio of the 4-hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer to the 5 -hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer is of > 0,0 to 1 to <100,0 to 1, preferred > 0,1 to <20,0 to 1 and more preferred > 0,2 to 1 to <5,0 to 1.
13. A process for producing a hydroxyl-group terminated oxazolidinone, wherein the solvent (D) and/or compound (B) is removed from the hydroxyl-group terminated oxazolidinone composition obtained according to one of claims 1 to 10 or the hydroxyl -group terminated oxazolidinone composition according to claim 11 or 12.
14. A hydroxyl-group terminated oxazolidinone obtainable according to claim 13.
15. The hydroxyl -group terminated oxazolidinone according to claim 14, wherein the molar ratio of the 4-hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer to the 5- hydroxymethyl substituted l,3-oxazolidin-2-one regioisomer is of > 0,0 to 1 to <100,0 to 1, preferred > 0,1 to <20,0 to 1 and more preferred > 0,2 to 1 to <5,0 to 1.
EP24732338.9A 2023-06-22 2024-06-17 Method for the production of a hydroxyl-group terminated oxazolidinone composition Pending EP4731688A1 (en)

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