CATALYSTS FOR THE SYNTHESIS OF OXAZOLIDINONES

Abstract

A catalyst for the synthesis of oxazolidinones, preferable polyoxazolidinones, comprising an N-heterocyclic carbene and a Lewis acid (L). The invention is also related to a process for the production of an oxazolidinone compound, preferably a polyoxazolidinone compound, by reacting an isocyanate compound, preferably a polyisocyanate compound with an epoxide compound, preferably a polyepoxide compound, in the presence of the N-heterocyclic carbene and a Lewis acid catalyst and also to the resulting polyoxazolidinone.

Claims

1. A catalyst for the synthesis of oxazolidinones, comprising an N-heterocyclic carbene and a Lewis acid (L).

2. The catalyst according to claim 1, wherein the catalyst comprises i) a mixture of a compound having the general formula (I), (II), (III), (IV), (V), or a mixture of any two or more thereof, with: formula (I) being: ##STR00013##  wherein R.sup.1 represents C.sub.1-C.sub.10 alkyl, C.sub.2-C.sub.10 alkenyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.6-C.sub.100 polyoxyalkylene, C.sub.5-C.sub.10 aryl or C.sub.5-C.sub.10 heteroaryl;  wherein A and D each independently represents a methylene moiety, CHR.sup.2, CR.sup.2R.sup.2, or A and D together represent a moiety from the series ethylene, propylene, butylene, 1,2-phenylene, R.sup.2—C═N—, —N═N—, C.sub.1-C.sub.10 alkyl, C.sub.2-C.sub.10 alkenyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.6-C.sub.100 polyoxyalkylene, C.sub.5-C.sub.10 aryl, C.sub.5-C.sub.10 hetaryl group-substituted 1,2-phenylene, —CH═N—, —CH.sub.2—NR.sup.2—, vinylene,  —CH.sub.2═CHR.sup.2—, —CHR.sup.2═CH.sub.2—, or —CHR.sup.2═CHR.sup.2—, wherein the moiety R.sup.2 has the meaning given above for R.sup.1;  and wherein E represents oxygen, sulfur, —NR.sup.3′- or —PR.sup.3′, wherein R.sup.3′ has the meaning given above for R.sup.1; formula (II) being: ##STR00014##  wherein R.sup.3 has the meaning given above in formula (I) for R.sup.1;  wherein A and D have the meaning given above in formula (I) for A and D;  wherein E has the meaning given above in formula (I) for E;  and wherein O stands mutually independently for oxygen, sulfur or N—R.sup.10,  wherein R.sup.10 has the meaning given above in formula (I) for R.sup.1; formula (III) being: ##STR00015##  wherein R.sup.4 has the meaning given above in formula (I) for R.sup.1;  wherein A and D have the meaning given above in formula (I) for A and D;  wherein E has the meaning given above in formula (I) for E;  and wherein R.sup.5 represents C.sub.1-C.sub.10 alkyl, C.sub.5-C.sub.12 cycloalkyl, C.sub.6-C.sub.100 polyoxyalkylene, or C.sub.5-C.sub.10 aryl; formula (IV) being: ##STR00016##  wherein R.sup.6 has the meaning given above in formula (I) for R.sup.1;  wherein A and D have the meaning given above in formula (I) for A and D;  wherein E has the meaning given above in formula (I) for E;  and wherein R.sup.7 represents C.sub.1-C.sub.10 perfluoroalkyl, perchloroalkyl, partially fluorinated C.sub.1-C.sub.10 alkyl, partially chlorinated C.sub.1-C.sub.10 alkyl,  perfluorinated C.sub.5-C.sub.10 aryl, partially fluorinated C.sub.5-C.sub.10 aryl, perchlorinated C.sub.5-C.sub.10 aryl, or partially chlorinated C.sub.5-C.sub.10 aryl; formula (V) being: ##STR00017##  wherein R.sup.8 has the meaning given above in formula (I) for R.sup.1;  wherein A and D have the meaning given above in formula (I) for A and D;  wherein E has the meaning given above in formula (I) for E;  and wherein X represents F.sup.−, Cl.sup.−, Br.sup.−, I, BF.sub.4.sup.−, PF.sub.6.sup.−, SbF.sub.6.sup.−, or HCO.sub.3.sup.−; and ii) a compound having the formula (VI) ##STR00018##  wherein R.sup.9 has the meaning given above in formula (I) for R.sup.1;  wherein A and D have the meaning given above in formula (I) for A and D;  wherein E has the meaning given above in formula (I) for E;  and wherein L is the Lewis acid.

3. A catalyst according to claim 2, wherein in formulae (I), (II), (III), (IV), (V) and (VI) the moieties R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.8,R.sup.9 and R.sup.10 each independently represent a methyl, ethyl, n-propyl, isopropyl, tert-butyl, neopentyl, isoamyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl or mesityl moiety; wherein R.sup.7 represents a CF3, CCl3, pentafluorophenyl, tetrafluorophenyl moiety; and wherein moieties A and D together represent an ethylene, vinylene or propylene moiety.

4. A catalyst according to claim 2, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.8, R.sup.9 and R.sup.19 each independently represents a methyl, isopropyl, phenyl or mesityl moiety.

5. A catalyst according to claim 1, wherein the Lewis acid comprises LiCl, LiBr, LiI, MgCl.sub.2, MgBr.sub.2, MgI.sub.2, SmI.sub.3, or a mixture of any two or more thereof.

6. A catalyst according to claim 1, wherein the N-heterocyclic carbene comprises one or more compounds having the formulae (II-1), (II-2), (II-3), (II-4), (II-5) and (II-6) ##STR00019##

7. A catalyst according to claim 1, wherein the molar ratio of Lewis acid to the N-heterocyclic carbene is 1:20 to 20:1.

8. A process for producing an oxazolidinone compound, comprising reacting an isocyanate compound with an epoxide compound in the presence of the catalyst according to claim 1.

9. The process according to claim 8, wherein the reaction is conducted at a reaction temperature of 80° C. to 300° C.

10. The process according to claim 8, wherein the isocyanate compound comprises a polyisocyanate compound comprising tetramethylene diisocyanate, 1,6-diisocyanatohexane, 2-methylpentamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate-, dodecanemethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate, diisocyanatodicyclohexylmethane, diphenylmethane diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldicyclohexylmethane, 4,4′-diisocyanato-2,2-dicyclohexyl propane, poly(hexamethylene diisocyanate), octamethylene diisocyanate, tolylene-α,4-diisocyanate, poly(propylene glycol) tolylene-2,4-diisocyanate terminated, poly(ethylene adipate) tolylene-2,4-diisocyanate terminated, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, poly[1,4-phenylene diisocyanate-co-poly(1,4-butanediol)] diisocyanate, poly(tetrafluoroethylene oxide-co-difluoromethylene oxide) α,ω-diisocyanate, 1,4-diisocyanatobutane, 1,8-diisocyanatooctane, 1,3-bis(1-isocyanato-1-methylethyl)benzene, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, naphthalene-1,5-diisocyanate, 1,3-phenylene diisocyanate, 1,4-diisocyanatobenzene, 2,4-, 2,5-, 2,6-diisocyanatotoluene, or a mixture thereof, 4,4′-, 2,4′-, 2,2′-diisocyanatodiphenylmethane, or a mixture thereof, 4,4′-, 2,4′-, or 2,2′-diisocyanato-2,2-diphenylpropane-p-xylene diisocyanate, α,α,α′,α′-tetramethyl- m- or -p-xylene diisocyanate, a biuret, isocyanurate or uretdione of any of the aforementioned isocyanates, or a mixture of any two or more thereof.

11. The process according to claim 8, wherein the epoxide compound comprises a polyepoxide compound comprising resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butandiol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-S diglycidyl ether, 9,9-bis(4-glycidyloxy phenyl)fluorine, tetrabromo bisphenol A diglycidyl ether, tetrachloro bisphenol A diglycidyl ether, tetramethyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetramethyl bisphenol-S diglycidyl ether, diglycidyl terephthalate, diglycidyl o-phthalate, 1,4-cyclohexane dicarboxylic acid diglycidyl ester, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, butadiene diepoxide, vinylcyclohexene diepoxide, limonene diepoxide, a diepoxide of a double unsaturated fatty acid C1-C18 alkyl ester, 2-dihydroxybenzene diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, 4,4′-(3,3,5-trimethylcyclohexyliden)bisphenyl diglycidyl ether, diglycidyl isophthalate, or a mixture of any two or more thereof.

12. A polyoxazolidinone compound comprising the reaction product of an aliphatic polyisocyanate compound with a polyepoxide compound in the presence of the catalyst according to claim 1, wherein the polyoxazolidinone compound has a theoretical number average molecular weight of ≥5000 to ≤500,000 g/mol, as determined with gel permeation chromatography (GPC).

13. A polyoxazolidinone compound comprising the reaction product of a polyisocyanate compound with an aliphatic polyepoxide compound in the presence of the catalyst according to claim 1, wherein the polyoxazolidinone compound has a theoretical number average molecular weight of ≥5000 to ≤500,000 g/mol, as determined with gel permeation chromatography (GPC).

14. A polyoxazolidinone compound the reaction product of an aliphatic polyisocyanate compound with an aliphatic polyepoxide compound in the presence of the catalyst according to claim 1, wherein the polyoxazolidinone compound has a theoretical number average molecular weight of ≥5000 to ≤500,000 g/mol, as determined with gel permeation chromatography (GPC).

15. (canceled)

16. The catalyst according to claim 5, wherein the Lewis acid comprises LiCl, LiBr, or a mixture thereof.

17. The catalyst according to claim 7, wherein the molar ratio of Lewis acid to the N-heterocyclic carbene is 1:5 to 5:1.

18. The catalyst according to claim 7, wherein the molar ratio of Lewis acid to the N-heterocyclic carbene is 1:2 to 2:1.

19. The process according to claim 8, wherein the isocyanate compound comprises a polyisocyanate compound and the epoxide compound comprises a polyepoxide compound.

Description

EXAMPLES

[0152] The present invention will be further described with reference to the following examples without wishing to be limited by them.

[0153] Isocyanate Compound

TABLE-US-00001 I-1: HDI 1,6-diisocyanatohexane, 99%, Covestro AG, Germany I-2: MDI 4,4-Methylene diphenyl diisocyanate (MDI 44), 98%, Covestro AG, Germany I-3: TDI 2,4-Toluenediisoyanate >99% 2,4-Isomer, Covestro AG, Germany I-4: IPDI Isophorone diisocyanate mixture of isomers) TCI, >99%, was used as received I-5: 12H-MDI 1-Isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexan (, mixture of isomers) TCI, >90%, was dried 18 h over CaH.sub.2 and was distilled under reduced pressure.

[0154] Epoxide Compound

TABLE-US-00002 E-1 BADGE 2-[[4-[2-[4-(Oxiran-2-ylmethoxy)phenyl]propan-2- yl]phenoxy]methyl]oxirane (Bisphenol A diglycidylether), difunctional epoxide, Epikote 162 (Hexion, 98%) was used as obtained without further purification. E-2: BDE 1,4-butandiol diglycidyl ether was received from TCI >93.0% and dried and distilled under reduced pressure from CaH.sub.2.

[0155] Catalyst

TABLE-US-00003 Lewis acid (L) LiCl: Lithium chloride, purity >99%, was obtained from Sigma Aldrich or LiCl für analytische Zwecke was provided by Grüssing GmbH, 99%. MgCl.sub.2 Magnesium chloride anhydrous for synthesis, ≥98%, Merck KGaA, Germany. Ph.sub.3MePBr TCI, >98% 1-Methylimidazole abcr GmbH Deutschland, 99%, was dried and distilled from CaH.sub.2

[0156] N-Heterocyclic Carbene Carboxylates

TABLE-US-00004 5u-Me-CO2 was synthesized according to the literature (Chem. Commun., 2003, 28-29) 6-iPr-CO2 was synthesized according to the literature (Chem, Eur. J., 2009, 15, 3103-3109; p. 3108) 6-Mes-CO2 was synthesized according to the literature (Chem, Eur. J., 2009, 15, 3103-3109; p. 3107-3108) 5u4,5Cl-Me-I was synthesized according to the literature (Organometallics 2007, 26, 6042-6049; p. 6047) 5u-Mes-Cl was synthesized according to the literature (Beilstein J. Org. Chem., 2007, 3, 22)

[0157] Solvents

[0158] Ortho-dichlorobenzene (o-DCB), 99%, anhydrous, was obtained from Sigma-Aldrich, Germany

[0159] Sulfolane, ≥99%, anhydrous, was obtained from Sigma-Aldrich, Germany or from abcr GmbH Deutschland, 99%.

[0160] 1,3-Dimethyl-2-imidazolidinone, was obtained from TCI, >99.0%. Before use it was dried and distilled under reduced pressure from CaH.sub.2 and degassed.

[0161] N,N-Dimethylacetamide, HPLC grade, 99.5% was obtained from Alfa Aesar.

[0162] Lithium bromide (LiBr) was obtained from abcr, 99.95%.

[0163] TDI, MDI, HDI, IPDI, LiCl, LiBr, MgCl.sub.2, N,N-Dimethylacetamide were used as received without further purification. BADGE (Epikote 162) was used after melting at 50° C. and drying over molecular sieves. 1,4-Butanediol diglycidyl ether was dried 18 h over CaH.sub.2 and distilled under reduced pressure, before degassing. Sulfolane (at 35° C.), o-DCB, NMP and 1,3-dimethylimidazolidin-2-one were dried for 18 h over CaH.sub.2 before vacuum distillation and degassing. Alternatively, o-DCB and sulfolane were dried over molecular sieves prior to use. BPGE and PTI were distilled prior to use. Alternatively, BPGE was used as received without further purification.

[0164] Molecular sieves (3 Å, Honeywell) were activated in a vacuum oven at 200° C. for 5 h prior to use.

[0165] Characterisation of Polyoxazolidinone

[0166] IR: Solid state IR analyses were performed on a Bruker ALPHA-P IR spectrometer equipped with a diamond probe head or a Bruker Platinum ATR. The software OPUS version 6.5 or 7.2 was used for data treatment. A background spectrum was recorded against ambient air. Thereafter, a small sample of the polyoxazolidinone (2 mg) was applied to the diamond probe and the IR spectrum recorded averaging over 24 spectra obtained in the range of 4000 to 400 cm.sup.−1 with a resolution of 4 cm.sup.−1.

[0167] Sample preparation: The reactions were prepared under inert nitrogen atmosphere or in a N.sub.2 filled glove box (Lab Master 130, MBraun, Garching, Germany). All reactions were executed with standard Schlenk technique under inert gas. After the reaction was completed the work up followed under ambient conditions.

[0168] Molecular Weight: The average chain length of the polyoxazolidinones was controlled by the molar ratio of diepoxide, diisocyanate and/or compound (D).

[0169] The formula below gives a general mathematical formula to calculate the average chain length n in the polymeric product obtained with a diisocyanate (A) and a bisepoxide (B):

n=(1+q)/(1+q−2pq)   (2)

[0170] with q=nx/ny≤1 and x,y=bisepoxide (B) or diisocyanate (A)

[0171] and with the conversion p whereby nx and ny are the molar amounts of bisepoxide or diisocyanate, respectively.

[0172] GPC: The number average molecular weight M.sub.n as well as the polydispersity index were determined by size exclusion chromatography in N,N-dimethylacetamide.

[0173] Parameters for size exclusion chromatography: [0174] System A: 1260 Infinity System from Agilent Technologies Inc.; solvent: N,N-dimethylacetamide (HPLC grade); sample concentration: 2-3 g/L; flow rate: 0.75 mL/min; calibration: poly(methylmethacrylate), 800 g/mol<Mp>201000 g/mol; columns PolarSil 8×50 mm, 35° C. (precolumn), PolarSil S linear 8×300 mm, 35° C.; detector: refractive index, 40° C.; software: Cirrus. This GPC was used to analyze examples 1 to 22. [0175] System B: 1260 system from Agilent; solvent: N,N-dimethylacetamide with LiBr (1.7 g/L); sample concentration: 2-3 g/L; flow rate: 1.0 mL/min at 60° C.; calibration: polystyrene, 370<Mp>2520000 g/mol and 800<Mp>2200000 g/mol; columns GRAM (precolumn), GRAM 3000, GRAM 3000, GRAM 100; detector: refractive index; software: PSS WinGPC Unity. This GPC was used to analyze examples 23 to 25.

[0176] Reactor

[0177] Small scale reactions were conducted in 4 mL glass vials equipped with a magnetic stirring bar and sealed with a septum. The vial was placed in a heatable aluminum block with drill holes. Below a magnetic stirrer was placed. This reaction setup was used for examples 1 to 22.

[0178] Larger scale reactions were conducted in a 500 ml double-walled glass reactor with mechanical stirring. Marlotherm SH (Azelis) was used as heating medium. This reaction setup was used for examples 23 to 25.

[0179] Oxazolidinone Synthesis

Procedure a)—Examples 1 to 10

Synthesis of Polyoxazolidinone Based on the Reaction of 1,6-diisocyanatohexane as Diisocyanate and Bisphenol A Diglycidyl Ether as Bisepoxide Using Various Combinations of Carbene Carboxylate and Lewis Acid as Catalytic System

[0180] The reactions shown in Table 1 entry 1 to 10 were carried out as follows: under inert gas 1 equivalent of the carbene carboxylate, 2 equivalents Lewis acid and 100 equivalents of the bisepoxide (0.2000 g, 0.588 mmol) were dissolved in sulfolane (0.75 g). The mixture was stirred at 200° C. Within 1 h a solution of 100 equivalents of diisocyanate in sulfolane (0.75 g) was added stepwise. The combined solutions were stirred for 2 h at 200° C., afterward the mixture was precipitated from propan-2-ol. The precipitate was centrifuged, the supernatant solution was decanted off and the remaining solid was dried under reduced pressure. The products were subsequently analyzed by GPC and IR.

Procedure β)—Examples 11 to 14

Synthesis of Polyoxazolidinone Based on the Reaction of 1,6 Diisocyanatohexane as Diisocyanate and Bisphenol A Diglycidyl Ether as Bisepoxide, Using Conceivable Catalysts as Catalytic System

[0181] The reactions shown in Table 1 were carried out as follows: under inert gas 2 equivalents of the conceivable catalyst were dissolved in sulfolane (0.5 g). The mixture was stirred at 200° C. Within 2 h a solution of 100 equivalents of the bisepoxide (0.2000 g, 0.588 mmol) and 100 equivalents of the diisocyanate in sulfolane (1.75 g) was added stepwise. The combined solutions were stirred for 1 h at 200° C., afterwards the mixture was precipitated from propan-2-ol. If a precipitate was found it was centrifuged, the supernatant solution was decanted off and the remaining solid was dried under reduced pressure. The products, if formed, were analyzed by IR spectroscopy.

[0182] The NHC structures and other conceivable molecules for comparison of the catalysts used and the corresponding abbreviation are shown in FIG. (XII).

##STR00012##

[0183] FIG. (XII): NHC structures and other conceivable molecules for comparison applied for synthesis of oxazolidinones Table 1

TABLE-US-00005 TABLE 1 Summary of examples for the synthesis of polyoxazolidinone based on the reaction of 1,6-diisocyanatohexane as diisocyanate and bisphenol A diglycidyl ether as bisepoxide, using various combinations of NHCs and Lewis acid as catalytic system, following the experimental procedure α). Iso- Lewis Iso Example cyanate Epoxy Carbene acid procedure cyanurate Mn PDI 1 HDI BADGE 6-iPr—CO2 LiCl α no 12000 5.3 2 HDI BADGE 6-iPr—CO2 MgC12 α no 10000 5.4 3 (comp.) HDI BADGE 6-iPr—CO2 — α yes — — 4 (comp.) HDI BADGE — LiCl α yes — — 5 (comp.) HDI BADGE — MgC12 α yes — — 6 HDI BADGE 6-Mes-CO2 LiCl α no 22000 5.4 7 (comp.) HDI BADGE 6-Mes-CO2 — α yes — — 8 HDI BADGE 5u-Me-CO2 LiCl α no  5000 8.3 9 HDI BADGE 5u-Me-CO2 MgC12 α no  9000 4.8 10 HDI BADGE 5u-Me-CO2 — α yes (comp.) 11 HDI BADGE 5u4,5-Cl-Me-I — β no no (comp.) reaction 12 HDI BADGE 5u-Mes-Cl — β yes — — (comp.) 13 HDI BADGE Me-Imi — β no no — (comp.) reaction 14 HDI BADGE Ph3MePBr — β no no — (comp.) reaction

Procedure γ) for Examples 15 to 22

[0184] The reactions, shown in Table 2, were executed as follows: Inside an MBraun glove box 1 equivalent of the carbene carboxylate (0.0008 g, 0.006 mmol) and 2 equivalents Lewis acid were dissolved in sulfolane (0.5 g) (or 1,3-dimethylimidazolidin-2-one (0.5 g)) (solution 1). 100 equivalents of the bisepoxide and 100 equivalents of the diisocyanate were dissolved in sulfolane (or 1,3-dimethylimidazolidin-2-one) (solution 2). Solution 1 was sealed with a septum. Solution 2 was filled in a syringe with a cannula. Both solutions were brought outside the glove box. Solution 1 was heated to 200° C. before solution 2 was added. The times in which solution 2 was added differed depending on the monomers and are given below in detail for each example. The combined solutions were stirred an additional hour at 200° C. The reaction solution was added to propan-2-ol. The precipitate was centrifuged, the supernatant solution was decanted off and the remaining solid was dried under reduced pressure.

[0185] The products were subsequently analyzed by GPC and IR.

Example 15

Synthesis of Polyoxazolidinone Based on Bisphenol A Diglycidyl Ether as Bisepoxide and 1,6-dasocyanatohexane as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ

[0186] Inside an MBraun glove box the following solutions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.2000 g bisphenol A diglycidyl ether (100 equivalents, 0.588 mmol) and 0.0988 g 1,6-diisocyanatohexane (100 eqiuvalents, 0.588 mmol) were dissolved in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 2 h (0.1 ml/7 min). Subsequently, the combined solutions were stirred 1 h at 200° C. The reaction solution was poured into 35 ml propan-2-ol and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 4-10 ml dichloromethane and precipitated from 35 ml propan-2-ol, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 72%. IR [cm.sup.−1]: 2966, 2930, 2866, 1735, 1607, 1582, 1508, 1491, 1450, 1361, 1243, 1182, 1055, 1037, 951, 828, 759, 733, 567. M.sub.n=32000 g/mol. PDI=2.7.

Example 16

Synthesis of Polyoxazolidinone Based on Bisphenol A Diglycidyl Ether as Bisepoxide and 4,4-methylene Diphenyl Diisocyanate as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ)

[0187] Inside an MBraun glove box the following solutions/suspensions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.2000 g bisphenol A diglycidyl ether (100 equivalents, 0.588 mmol) and 0.1470 g diphenyl methane-4,4′-diisocyanate (MDI) (100 eqiuvalents, 0.588 mmol) were homogeneously suspended in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 4 h (0.1 ml/14 min). Subsequently, the combined solutions were stirred 1 h at 200° C. The reaction solution was poured into 35 ml propan-2-ol and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 5-10 ml dimethylformamide or dimethyl sulfoxide and precipitated from 35 ml propan-2-ol, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 71%. IR [cm.sup.−1]: 2964, 1741, 1697, 1509, 1430, 1406, 1309, 1220, 1183, 1133, 1030, 983, 950, 828, 751, 571, 511. M.sub.n=14000 g/mol. PDI=2.7.

Example 17

Synthesis of Polyoxazolidinone Based on Bisphenol A Diglycidyl Ether as Bisepoxide and Isophorone Diisocyanate as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ)

[0188] Inside an MBraun glove box the following solutions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.2000 g bisphenol A diglycidyl ether (100 equivalents, 0.588 mmol) and 0.1306 g isophorone diisocyanate (100 eqiuvalents, 0.588 mmol) were dissolved in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 2 h (0.1 ml/7 min). Subsequently, the combined solutions were stirred 1 h at 200° C. The reaction solution was added to 35 ml propan-2-ol and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 4-10 ml dichloromethane and precipitated from 35 ml propan-2-ol, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 69%. IR [cm.sup.−1]: 2960, 1737, 1607, 1508, 1431, 1234, 1182, 1058, 1031, 951, 829, 761, 736, 694, 565. M.sub.n=31000 g/mol. PDI=1.9.

Example 18

Synthesis of Polyoxazolidinone Based on Bisphenol a Diglycidyl Ether as Bisepoxide and Dicyclohexyl methane-4,4-diisocyanate as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ)

[0189] Inside an MBraun glove box the following solutions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.2000 g bisphenol A diglycidyl ether (100 equivalents, 0.588 mmol) and 0.1541 g dicyclohexyl methane-4,4′-diisocyanate (100 eqiuvalents, 0.588 mmol) were dissolved in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 2 h (0.1 ml/7 min). Subsequently, the combined solutions were stirred 1 h at 200° C. The reaction solution was poured into 35 ml propan-2-ol and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 4-10 ml dichloromethane and precipitated from 35 ml propan-2-ol, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 73%. IR [cm.sup.−1]: 2924, 2854, 1734, 1607, 1508, 1430, 1377, 1299, 1233, 1182, 1106, 1057, 951, 902, 828, 761, 734, 700, 567. M.sub.n=32000 g/mol. PDI=2.5.

Example 19

Synthesis of Polyoxazolidinone Based on Bisphenol A Diglycidyl Ether as Bisepoxide and toluene-2,4-diisocyanate as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ)

[0190] Inside an MBraun glove box the following solutions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g 1,3-dimethylimidazolidin-2-one (solution 1). 0.2000 g bisphenol A diglycidyl ether (100 equivalents, 0.588 mmol) and 0.1023 g toluene-2,4-diisocyanate (tdi) (100 eqiuvalents, 0.588 mmol) were dissolved in 1.75 g 1,3-dimethylimidazolidin-2-one (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 4 h (0.1 ml/14 min). Subsequently, the combined solutions were stirred for 1 h at 200° C. The reaction solution was poured into 35 ml propan-2-ol and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 5-10 ml dimethylformamide or dimethyl sulfoxide and precipitated from 35 ml propan-2-ol, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 89%. IR [cm.sup.−1]: 2966, 1742, 1608, 1507, 1410, 1222, 1183, 1093, 1025, 950, 828, 754, 684, 555. M.sub.n=11000 g/mol. PDI=2.4.

Example 20

Synthesis of Polyoxazolidinone Based on Bisphenol A Diglycidyl Ether as Bisepoxide and Both, 1,6-diisocyanatohexane and 4,4-methylene Diphenyl Diisocyanate as Diisocyanates, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ

[0191] Inside an MBraun glove box the following solutions/suspensions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.2000 g bisphenol A diglycidyl ether (100 equivalents, 0.588 mmol), 0.0494 g 1,6-diisocyanatohexane (50 eqiuvalents, 0.294 mmol) and 0.0735 g diphenyl-4,4′-diisocyanate (50 equivalents, 0.294 mmol) were dissolved/suspended in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 4 h (0.1 ml/14 min). Subsequently, the combined solutions were stirred for 1 h at 200° C. The reaction solution was poured into 35 ml propan-2-ol and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 4-10 ml dichloromethane and precipitated from 35 ml propan-2-ol, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 92%. IR [cm.sup.−1]: 2966, 2928, 1740, 1607, 1508, 1453, 1430, 1407, 1299, 1222, 1182, 1130, 1106, 983, 950, 827, 753, 732, 557, 511. M.sub.n=31000 g/mol. PDI=2.5.

Example 21

Synthesis of Polyoxazolidinone Based on 1,4-butanediol Diglycidyl Ether as Bisepoxide and 1,6-diisocyanatohexane as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ

[0192] Inside an MBraun glove box the following solutions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.1188 g 1,4-butanediol diglycidyl ether (100 equivalents, 0.588 mmol) and 0.0988 g 1,6-hexane diisocyanate (100 eqiuvalents, 0.588 mmol) were dissolved in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 2 h (0.1 ml/7 min). Subsequently, the combined solutions were stirred 1 h at 200° C. The reaction solution was poured into 35 ml demineralized water and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 5-10 ml dimethylformamide or dimethyl sulfoxide and precipitated from 35 ml demineralized water, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 52%. IR [cm.sup.−1]: 2928, 1731, 1490, 1444, 1358, 1254, 1121, 1057, 762, 682. M.sub.n=9000 g/mol. PDI=2.0.

Example 22

Synthesis of Polyoxazolidinone Based on 1,4-butanediol Diglycidyl Ether as Bisepoxide and 4,4-methylene Diphenyl Diisocyanate as Diisocyanate, 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) as Carbene Carboxylate and Lithium Chloride as Lewis Acid, Following Procedure γ

[0193] Inside an MBraun glove box the following solutions were prepared: 0.0008 g 1,3-dimethylimidazolium-2-carboxylate (1 equivalent, 0.006 mmol) and 0.0005 g lithium chloride (2 equivalents, 0.012 mmol) were dissolved in 0.5 g sulfolane (solution 1). 0.1188 g 1,4-butanediol diglycidyl ether (100 equivalents, 0.588 mmol) and 0.1470 g diphenylmethane-4,4′-diisocyanate (100 eqiuvalents, 0.588 mmol) were dissolved in 1.75 g sulfolane (solution 2). Solution 1, in a 4 ml-screw top jar, was sealed with a septum. Solution 2 was filled in a 3 ml-syringe with a cannula. Both solutions were brought outside the box. Solution 1 was heated to 200° C. before solution 2 was added during 4 h (0.1 ml/14 min). Subsequently, the combined solutions were stirred 1 h at 200° C. The reaction solution was poured into 35 ml demineralized water and a colorless solid precipitated, the mixture was centrifuged (4000 rpm, 99 min), the supernatant solution was discarded and the remaining solid was dried under reduced pressure. In case further purification was necessary the solid was dissolved in 5-10 ml dimethylformamide or dimethyl sulfoxide and precipitated from 35 ml demineralized water, centrifuged, the supernatant solution was discarded and the remaining solid was dried under reduced pressure. Yield: 76%. IR [cm.sup.−1]: 2866, 1738, 1612, 1513, 1481, 1429, 1405, 1311, 1219, 1129, 983, 856, 813, 799, 752, 650, 594, 512. M.sub.n=9000 g/mol. PDI=3.0.

TABLE-US-00006 TABLE 2 Summary of experiments for the synthesis of polyoxazolidinone based on various diisocyanates and bisphenol A diglycidyl ether as bisepoxide, using 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) and lithium chloride as catalytic system, following the experimental procedure γ Iso- Lewis cyanurare Mn Example Isocyanate Epoxide Carbene acid Trimer [g/mol] PDI 15 HDI BADGE 5u-Me-CO2 LiCl no 32000 2.7 16 MDI BADGE 5u-Me-CO2 LiCl no 14000 2.7 17 IPDI BADGE 5u-Me-CO2 LiCl no 31000 1.9 18 12H-MDI BADGE 5u-Me-CO2 LiCl no 32000 2.5 19 TDI BADGE 5u-Me-CO2 LiCl no 11000 2.4 20 HDI/MDI BADGE 5u-Me-CO2 LiCl no 31000 2.5 21 HDI BDE 5u-Me-CO2 LiCl no 9000 2.0 22 MDI BDE 5u-Me-CO2 LiCl no 9000 3.0

Procedure δ) for Examples 23 to 25

Example 23

Synthesis of Polyoxazolidinone Based on 4,4-methylene Diisocyanate as Diisocyanate and Bisphenol A Diglycidyl Ether as Bisepoxide, Using 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) and Lithium Chloride in the Molar Ratio 1/2 as Catalytic System, Following the Experimental Procedure δ

[0194] Under a continuous flow of nitrogen, a glass flask (500 mL) was charged with LiCl (0.0999 g), 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2, 0,1653 g) and sulfolane (28 mL) and stirred at 175° C. for 15 min. Subsequently, ortho-dichlorobenzene (95 mL) was added. A glass flask (200 mL) was charged with methylene diphenyl diisocyanate (29.4920 g), para-tert-butylphenyl glycidyl ether (1.9448 g), bisphenol A glycidyl ether (38.5126 g), and 85 mL ortho-dichlorobenzene. The monomer solution was added slowly to the catalyst solution within 90 min. After the addition was finished, the reaction was stirred at 175° C. for another 30 min. After a total reaction time of 120 min, para-tert-butylphenyl glycidyl ether (4.8620 g), dissolved in ortho-dichlorobenzene (10 mL), was added to the reaction solution. After the addition, the reaction was stirred at 175° C. for another 3 h. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum of the reaction mixture. Subsequently, 112 mL of N-methyl pyrrolidone were added to the reaction solution and the mixture was cooled to ambient temperature. The precipitation of the polymer was performed in ethanol at ambient temperature: The solution (50 mL) was added slowly into 400 mL of ethanol and milled with an ultraturrax dispersing instrument. The product was washed with ethanol, filtered, and dried at ambient temperature overnight. Subsequently, the product was dried under vacuum at 200° C. for 6 h.

[0195] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1750 cm.sup.−1. The final product was characterized by GPC.

Example 24

Synthesis of Polyoxazolidinone Based on 4,4-methylene Diisocyanate as Diisocyanate and Bisphenol A Diglycidyl Ether as Bisepoxide, Using 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) and Lithium Chloride in the Molar Ratio 1/1 as Catalytic System, Following the Experimental Procedure 8

[0196] Under a continuous flow of nitrogen, a glass flask (500 mL) was charged with LiCl (0.0999 g), 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2, 0.3304 g) and sulfolane (28 mL) and stirred at 175° C. for 15 min. Subsequently, ortho-dichlorobenzene (95 mL) was added. A glass flask (200 mL) was charged with methylene diphenyl diisocyanate (29.4920 g), para-tert-butylphenyl glycidyl ether (1.9448 g), bisphenol A glycidyl ether (38.5126 g), and 85 mL ortho-dichlorobenzene. The monomer solution was added slowly to the catalyst solution within 90 min. After the addition was finished, the reaction was stirred at 175° C. for another 30 min. After a total reaction time of 120 min, para-tert-butylphenyl glycidyl ether (4.8620 g), dissolved in ortho-dichlorobenzene (10 mL), was added to the reaction solution. After the addition, the reaction was stirred at 175° C. for another 3 h. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum of the reaction mixture. Subsequently, 112 mL of N-methyl pyrrolidone were added to the reaction solution and the mixture was cooled to ambient temperature. The precipitation of the polymer was performed in ethanol at ambient temperature: The solution (50 mL) was added slowly into 400 mL of ethanol and milled with an ultraturrax dispersing instrument. The product was washed with ethanol, filtered, and dried at ambient temperature overnight. Subsequently, the product was dried under vacuum at 200° C. for 6 h.

[0197] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1750 cm.sup.−1. The final product was characterized by GPC.

Example 25

Synthesis of Polyoxazolidinone Based on 4,4-methylene Diisocyanate as Diisocyanate and Bisphenol A Diglycidyl Ether as Bisepoxide, Using 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) and Lithium Chloride in the Molar Ratio 2/1 as Catalytic System, Following the Experimental Procedure 8

[0198] Under a continuous flow of nitrogen, a glass flask (500 mL) was charged with LiCl (0.0999 g), 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2, 0,6606 g) and sulfolane (28 mL) and stirred at 175° C. for 15 min. Subsequently, ortho-dichlorobenzene (95 mL) was added. A glass flask (200 mL) was charged with methylene diphenyl diisocyanate (29.4920 g), para-tert-butylphenyl glycidyl ether (1.9448 g), bisphenol A glycidyl ether (38.5126 g), and 85 mL ortho-dichlorobenzene. The monomer solution was added slowly to the catalyst solution within 90 min. After the addition was finished, the reaction was stirred at 175° C. for another 30 min. After a total reaction time of 120 min, para-tert-butylphenyl glycidyl ether (4.8620 g), dissolved in ortho-dichlorobenzene (10 mL), was added to the reaction solution. After the addition, the reaction was stirred at 175° C. for another 3 h. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum of the reaction mixture. Subsequently, 112 mL of N-methyl pyrrolidone were added to the reaction solution and the mixture was cooled to ambient temperature. The precipitation of the polymer was performed in ethanol at ambient temperature: The solution (50 mL) was added slowly into 400 mL of ethanol and milled with an ultraturrax dispersing instrument. The product was washed with ethanol, filtered, and dried at ambient temperature overnight. Subsequently, the product was dried under vacuum at 200° C. for 6 h.

[0199] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1750 cm.sup.−1. The final product was characterized by GPC.

TABLE-US-00007 TABLE 3 Summary of experiments for the synthesis of polyoxazolidinone based on 4,4-methylene diisocyanate as diisocyanate and bisphenol A diglycidyl ether as bisepoxide, using various ratios of 1,3-dimethylimidazolium-2-carboxylate (5u-Me-CO2) and lithium chloride as catalytic system, following the experimental procedure δ. For GPC measurement of examples 23-25, the GPC system B was employed. Ratio Lewis NHC/L Mn Example Isocyanate Epoxide Carbene acid [mol/mol] Trimer [g/mol] PDI 23 MDI BADGE 5u-Me-CO2 LiCl 1/2 no 6900 4.0 24 MDI BADGE 5u-Me-CO2 LiCl 1/1 no 7800 3.6 25 MDI BADGE 5u-Me-CO2 LiCl 2/1 no 1900 4.3