METHOD FOR THE PRODUCTION OF THERMOPLASTIC POLYOXAZOLIDINONE POLYMERS

Abstract

A process for producing thermoplastic polyoxazolidinone comprising copolymerization of a diisocyanate compound (A) with a bisepoxide compound (B) in the presence of a catalyst (C) and a compound (D) in a solvent (E), wherein the bisepoxide compound (B) comprises isosorbide diglycidylether, wherein the catalyst (C) is selected from the group consisting of alkali halogenides and earth alkali halogenides, and transition metal halogenides, compound (D) is selected from the group consisting of monofunctional isocyanate, monofunctional epoxide, and

wherein the process comprises step (α) of placing the solvent (E) and the catalyst (C) in a reactor to provide a mixture, and adding the diisocyanate compound (A), the bisepoxide compound (B) and the compound (D) in step (β) to the mixture resulting from the step (α). The invention is also related to the resulting thermoplastic polyoxazolidinone.

Claims

1. A process for producing a thermoplastic polyoxazolidinone comprising copolymerizing a diisocyanate compound with a bisepoxide compound in the presence of components comprising a catalyst, and a chain regulator and a solvent, wherein the bisepoxide compound comprises isosorbide diglycidylether, the catalyst comprises an alkali halogenide, an earth alkali halogenide, a transition metal halogenide or a mixture thereof, the chain regulator comprises a monofunctional isocyanate, a monofunctional epoxide, or a mixture thereof, and wherein the process comprises: (α) placing the solvent and the catalyst in a reactor to provide a mixture, and (β) adding the diisocyanate compound, the bisepoxide compound and the chain regulator to the mixture resulting from step (α).

2. The process according to claim 1, wherein the diisocyanate compound, the bisepoxide compound and the chain regulator are added in a continuous manner to the mixture of step (α).

3. The process according to claim 1, wherein the diisocyanate compound, the bisepoxide compound and the chain regulator are added in a step-wise manner to the mixture of step (α).

4. The process according to claim 1, wherein the diisocyanate compound, the bisepoxide compound and the chain regulator are mixed prior to addition to the mixture resulting from step (α).

5. The process according to claim 4, wherein the mixture of the diisocyanate compound, the bisepoxide compound and the chain regulator is added in a continuous manner to the mixture of step (α).

6. The process according to claim 4, wherein the mixture of the diisocyanate compound, the bisepoxide compound and the chain regulator is added in a step-wise manner with two or more individual addition steps to the mixture of step (α).

7. The process according to claim 1, wherein the solvent comprising a polar aprotic solvent.

8. The process according to claim 1, wherein the catalyst comprises LiCl, LiBr, LiI, MgCl.sub.2, MgBr.sub.2, MgI.sub.2, SmI.sub.3, or a mixture thereof.

9. The process according to claim 1, wherein the chain regulator comprises phenyl glycidyl ether, o-kresyl glycidyl ether, m-kresyl glycidyl ether, p-kresyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, glycidyl benzoate, glycidyl acetate, glycidyl cyclohexylcarboxylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidylether, a C10-C18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1,2-butene oxide, 2,3-butene oxide, 1,2-hexene oxide, an oxide of a C10-C18 alpha-olefin, cyclohexene oxide, vinylcyclohexene monoxide, limonene monoxide, butadiene monoepoxide, N glycidyl phthalimide, n hexylisocyanate, 4-tert-butylphenyl glycidyl ether, cyclohexyl isocyanate, ω-chlorohexamethylene isocyanate, 2-ethyl hexyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, stearyl isocyanate, methyl isocyanate, ethyl isocyanate, butyl isocyanate, isopropyl isocyanate, octadecyl isocyanate, 6-chloro-hexyl isocyanate, cyclohexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethylcyclohexyl isocyanate, 2-norbornyl methyl isocyanate, decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, 3-butoxypropyl isocyanate, 3-(2-ethylhexyloxy)-propyl isocyanate, (trimethylsilyl)isocyanate, phenyl isocyanate, ortho-, meta-, para-tolyl isocyanate, chlorophenyl isocyanate (2,3,4-isomers), dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenylisocyanate, 4-dodecylphenylisocyanat, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-t-butyl phenyl isocyanate, 1-naphthyl isocyanate, or a mixture of any two or more thereof.

10. The process according to claim 7, wherein the polar aprotic solvent comprises sulfolane, dimethylsulfoxide, and gamma-butyrolactone, or a mixture thereof.

11. The process according to claim 1, further comprising reacting the polyoxazolidinone with an alkylene oxide.

12. The process according to claim 11, wherein the alkylene oxide comprises a monofunctional alkylene oxide.

13. The process according to claim 12, wherein the monofunctional alkylene oxide comprises phenyl glycidyl ether, o-kresyl glycidyl ether, m-kresyl glycidyl ether, p-kresyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 4-chlorophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, glycidyl benzoate, glycidyl acetate, glycidyl cyclohexylcarboxylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidylether, a C10-C18 alkyl glycidyl ether, allyl glycidyl ether, ethylene oxide, propylene oxide, styrene oxide, 1,2-butene oxide, 2,3-butene oxide, 1,2-hexene oxide, an oxide of a C10-C18 alpha-olefin, cyclohexene oxide, vinylcyclohexene monoxide, limonene monoxide, butadiene monoepoxide N-glycidyl phthalimide, 4-tert-butylphenyl glycidyl ether, or a mixture of any two or more thereof.

14. A thermoplastic polyoxazolidinone obtained by the process of claim 11.

15. The thermoplastic polyoxazolidinone according to claim 14, wherein the thermoplastic polyoxazolidinone has a number average molecular weight of 500 to 500,000 g/mol.

16. A process for producing thermoplastic polyoxazolidinones comprising copolymerization of a diisocyanate compound with a bisepoxide compound in the presence of components comprising a catalyst, a chain regulator comprising a monofunctional epoxide, a monofunctional isocyanate, or a mixture thereof, and a solvent composition, wherein the bisepoxide compound comprises isosorbide diglycidylether, the catalyst comprises an alkali halogenide, an earth alkali halogenide, or a transition metal halogenide, and wherein the process comprises: (a) providing a solution of the diisocyanate compound, the bisepoxide compound, the chain regulator and a solvent, (b) placing solvent and the catalyst in a reactor to provide a mixture, and (c) adding the solution provided in step (a) to the mixture resulting from step (b).

17. The process according to claim 16, wherein the solvent composition comprises a polar aprotic solvent comprising sulfolane, dimethylsulfoxide, gamma-butyrolactone, or a combination of two or more thereof.

18. The process of claim 16, wherein the process is performed at a reaction temperature of ≥130° C. to ≤280° C. and a reaction time of 1 hour to 6 hours.

Description

EXAMPLES

[0109] The present invention will be further described with reference to the following examples without wishing to be limited by them.

Diisocyanate Compound (A)

[0110] A-2: 2,4-Toluenediisoyanate >99% (TDI) 2,4-Isomer, Covestro AG, Germany

Epoxide Compound (B)

[0111] B-1 ISDGE 1,4:3,6-Dianhydro-2,5-bis-O-(2,3-epoxypropyl)-D-Glucitol, difunctional epoxide (purity 97%) was synthesized in a 2-step procedure in accordance to the literature (J. Lukaszczyk, B. Janicki, A. López, K. Skolucka, H. Wojdyla, C. Persson, S. Piaskowski, M. Śmiga-Matuszowicz “Novel injectable biomaterials for bone augmentation based on isosorbide dimethacrylic monomers”). Isosorbide (TCI Germany; purity >98%) was treated with allyl bromide and an aqueous KOH solution to generate diallyl isosorbide. Purification was achieved by using vacuum distillation. The purified compound was then treated with OXONE® to yield the corresponding diepoxide. [0112] B-2 BADGE 2-[[4-[2-[4-(Oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane (Bisphenol A diglycidyl ether), difunctional epoxide, Epikote 162 (Hexion, 98%) was used as obtained without further purification.

Catalyst (C)

[0113] C-1: LiBr Lithium bromide, purity >99.9%, was obtained from Sigma Aldrich [0114] C-2: Ph.sub.4PBr Tetraphenyl phosphonium bromide, >97%, was obtained by Sigma Aldrich

Solvents (E)

[0115] Ortho-dichlorobenzene (o-DCB), purity 99%, anhydrous, was obtained from Sigma-Aldrich, Germany [0116] N-Methylpyrrolidone (NMP), purity 99.5%, anhydrous, was obtained from Sigma-Aldrich, Germany

Sulphur Containing Solvent (E-1)

[0117] Sulfolane, purity ≥99%, anhydrous, was obtained from Sigma-Aldrich, Germany

Compound (D) and (F)

[0118] BPGE para-tert-butylphenylglycidylether (92%, Denacol EX-146, Nagase Chem Tex Corporation, Japan), was distilled before use (>99%)

[0119] TDI, NMP, LiBr, and BPGE were used as received without further purification. BADGE (Epikote 162) and sulfolane were used after melting at 50° C. and drying over molecular sieve. o-DCB was dried over molecular sieve prior to use.

[0120] Addition protocol 1: Solution of diisocyanate compound (A) is added to a solution of bisepoxide compound (B) and the catalyst (C) in a semi-batch process, the compound (D) is added in a second step according to example 14 of EP 16703330.7.

[0121] Addition protocol 2: The diisocyanate compound (A), the bisepoxide compound (B) and the compound (D) is added to a flask containing the catalyst (C) dissolved in the solvent (E) comprising the solvent (E-1) according to claim 1 of the present application.

Characterisation of Polyoxazolidinone

IR

[0122] Solid state IR analyses were performed on a Bruker ALPHA-P IR spectrometer equipped with a diamond probe head. The software OPUS 6.5 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.

NMR

[0123] For .sup.1H NMR analysis, a sample of the oligomer (20 mg) was dissolved in deuterated dimethyl sulfoxide (0.5 mL) and measured on a Bruker spectrometer (AV400, 400 MHz).

Molecular Weight

[0124] The average chain length of the thermoplastic polyoxazolidinones was controlled by the molar ratio of bisepoxide (B), diisocyanate (A) and/or compound (D).

[0125] 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)

with q=n.sub.x/n.sub.y≤1 and x,y=bisepoxide (B) or diisocyanate (A) and with the conversion p

whereby n.sub.x and n.sub.y are the molar amounts of bisepoxide or diisocyanate, respectively.

DSC

[0126] The glass transition point T.sub.g was recorded on a Mettler Toledo DSC 1. The sample (4 to 10 mg) was heated from 30° C. to 250° C. at a heating rate of 10 K/min then cooled down to 30° C. at a rate of 10 K/min. This heating cycle was repeated three times. For data analysis the software STAR© SW 11.00 was used. For determination of the glass transition temperature a tangential analysis method was used. The glass transition temperature T.sub.g was recorded on a Mettler Toledo DSC 1. The sample (4 to 10 mg) was heated from 30° C. to 250° C. at a heating rate of 10 K/min then cooled down to 30° C. at a rate of 10 K/min. This heating cycle was repeated three times. For data analysis the software STAR© SW 11.00 was used. For determination of the glass transition temperature the inflect point was used and taken from the third heating cycle.

TGA

[0127] The stability of the thermoplastic polyoxazolidinones was characterized by thermogravimetric analysis (TGA). The measurements were performed on a Mettler Toledo TGA/DSC 1. For data analysis the software STAR© SW 11.00 was used. The sample (6 to 20 mg) was weighed in a 70 μL Alox pan (previously cleaned at 1000° C. for 7 hrs), heated from 25° C. to 600° C. with a heating rate of 10 K/min under argon flow (15 mL/min) and the relative weight loss was followed in dependence of temperature. For data analysis the software STAR© SW 11.00 was used. The decomposition temperature (T.sub.d) stated is the onset point determined from the step tangent of the sinusoidal weight loss curve. To study the thermal stability over time, the thermoplastic polyoxazolidinones samples (6 to 20 mg) were weighed in a 150 μL Alox pan (previously cleaned at 1000° C. for 7 hrs), heated from 25° C. to the target temperature (240° C., 260° C. and 280° C., respectively) with a heating rate of 10 K/min under argon flow (15 mL/min) followed by an isothermal heating for 1 h at the corresponding target temperature. The relative weight loss was followed in dependence of time. The Δwt %.sup.T given in the examples is the weight loss percentage of the sample after 1 h at the target temperature T.

GPC

[0128] The determination of the number average molecular weights, weight average molecular weights and the polydispersity index were carried out by gel permeation chromatography (GPC). GPC was performed on an Agilent 1100 Series instrument with DMAc+LiBr (1.7 g.Math.L.sup.−1) as the eluent, PSS GRAM analytical columns (1×100 Å, 2×3000 Å) from PSS, equipped with a refractive index (RI) detector. The column flow rate in all measurements was set to 0.675 mL.Math.min.sup.−1. For determining molecular weights, the calibration was performed with poly(styrene) standards (ReadyCal-Kit PS-Mp 370-2520000Da from PSS). The samples were analysed using PSS

[0129] WinGPC UniChrom V 8.2 Software.

Example 1: Polymerization of TDI as Compound (A) and ISDGE as Compound (B) Using LiBr as Compound (C) and BPGE as Compound (D) with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0130] A Schlenk flask was charged with lithium bromide (0.01 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol), ISDGE (1.51 g, 5.63 mmol) and BPGE (0.05 g, 0.23 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min at this temperature additional o-DCB (2.0 mL) was added and stirred for 30 min. Subsequently 10 mL of N-methyl pyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction mixture. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed. In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1742 cm.sup.−1.

[0131] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was not observed.

[0132] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0133] Thermogravimetric analysis of the product showed a mass loss of 0.6 wt % after tempering at 240° C. for 1 h and a mass loss of 0.8 wt % after tempering at 260° C. for 1 h.

Example 2: Polymerization of TDI as Compound (A) and ISDGE as Compound (B) Using LiBr as Compound (C) with BPGE as Compound (D) and Addition of a Compound (F) Added in a Second Step with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0134] A Schlenk flask was charged with LiBr (0.01 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol), ISDGE (1.51 g, 5.63 mmol) and BPGE (0.05 g, 0.23 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min, para-tert-butylphenyl glycidyl ether (0.24 g, 1.15 mmol), dissolved in ortho-dichlorobenzene (2.0 mL), was added to the reaction solution. After the addition, the reaction was stirred at 175° C. for another 30 min. Subsequently 10 mL of N-methylpyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature.

[0135] The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction mixture.

[0136] The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed.

[0137] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1740 cm.sup.−1.

[0138] In the solid state IR spectrum the characteristic signal for isocyanurate groups was not observed. In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0139] Thermogravimetric analysis of the product showed a mass loss of 0.4 wt % after tempering at 240° C. for 1 h and a mass loss of 0.5 wt % after tempering at 260° C. for 1 h.

Example 3: Polymerization of TDI as Compound (A) and ISDGE as Compound (B) with LiBr as Compound (C) Using BPGE as (D) with Addition Protocol 1 and Sulfolane as Solvent (E-1)

[0140] A Schlenk flask was charged with LiBr (0.01 g, 0.12 mmol), ISDGE (1.51 g, 5.63 mmol) and BPGE (0.05 g, 0.23 mmol). Then sulfolane (0.63 mL) and o-DCB (1.56 mL) were added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol) in o-DCB (3.12 mL) was added at a rate of 1 mL/min. After 30 min, the stirring stopped due to gelification in the Schlenk flask.

[0141] Analysis of the reaction mixture by IR spectroscopy showed uncomplete conversion of the isocyanate groups (2260 cm.sup.−1).

[0142] The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed.

[0143] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1740 cm.sup.−1.

[0144] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was observed.

[0145] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

Example 4: Polymerization of TDI as Compound (A) and ISDGE as Compound (B) with Ph.SUB.4.PBr as Compound (C) Using BPGE as (D) with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0146] A Schlenk flask was charged with tetraphenyl phosphonium bromide (0.05 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol), ISDGE (1.51 g, 5.63 mmol) and BPGE (0.05 g, 0.23 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min at this temperature additional o-DCB (2.0 mL) was added and stirred for 30 min. Subsequently 10 mL of N-methyl pyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature.

[0147] The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax mixture. The dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed.

[0148] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1742 cm.sup.−1.

[0149] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was observed.

[0150] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0151] Thermogravimetric analysis of the product showed a mass loss of 0.8 wt % after tempering at 240° C. for 1 h and a mass loss of 1.1 wt % after tempering at 260° C. for 1 h.

Example 5: Polymerization of TDI as Compound (A) and ISDGE as Compound (B) Using LiBr as Compound (C) with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0152] A Schlenk flask was charged with lithium bromide (0.01 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol) and ISDGE (1.51 g, 5.63 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min at this temperature additional o-DCB (2.0 mL) was added and stirred for 30 min. Subsequently 10 mL of N-methyl pyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature.

[0153] The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction mixture. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed.

[0154] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1742 cm.sup.−1.

[0155] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was not observed.

[0156] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0157] Thermogravimetric analysis of the product showed a mass loss of 0.8 wt % after tempering at 240° C. for 1 h and a mass loss of 1.1 wt % after tempering at 260° C. for 1 h.

Example 6: Polymerization of TDI as Compound (A) ISDGE and BADGE as Compound (B) with LiBr as Compound (C) Using BPGE as Compound (D) and Addition of a Compound (F) Added in a Second Step with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0158] A Schlenk flask was charged with lithium bromide (0.01 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol), ISDGE (0.75 g, 2.81 mmol), BADGE (0.96 g, 2.81 mmol) and BPGE (0.05 g, 0.23 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min, para-tert-butylphenyl glycidyl ether (0.24 g, 1.15 mmol), dissolved in o-DCB (2.0 mL), was added to the reaction solution and stirred for 30 min. Subsequently 10 mL of N-methyl pyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature.

[0159] The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction mixture. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed.

[0160] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm.sup.−1.

[0161] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was not observed.

[0162] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0163] Thermogravimetric analysis of the product showed a mass loss of 0.2 wt % after tempering at 240° C. for 1 h and a mass loss of 0.3 wt % after tempering at 260° C. for 1 h.

Example 7: Polymerization of TDI as Compound (A) ISDGE and BADGE as Compound (B) with LiBr as Compound (C) Using BPGE as Compound (D) and Addition of a Compound (F) Added in a Second Step with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0164] A Schlenk flask was charged with lithium bromide (0.01 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol), ISDGE (0.30 g, 1.13 mmol), BADGE (1.53 g, 4.52 mmol) and BPGE (0.05 g, 0.23 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min, para-tert-butylphenyl glycidyl ether (0.24 g, 1.15 mmol), dissolved in o-DCB (2.0 mL), was added to the reaction solution and stirred for 30 min. Subsequently 10 mL of N-methyl pyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature.

[0165] The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction mixture. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed. In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1748 cm.sup.−1.

[0166] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was not observed.

[0167] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0168] Thermogravimetric analysis of the product showed a mass loss of 0.2 wt % after tempering at 240° C. for 1 h and a mass loss of 0.3 wt % after tempering at 260° C. for 1 h.

Example 8: Polymerization of TDI as Compound (A) ISDGE and BADGE as Compound (B) with LiBr as Compound (C) Using BPGE as Compound (D) and Addition of a Compound (F) Added in a Second Step with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0169] A Schlenk flask was charged with lithium bromide (0.01 g, 0.12 mmol). Then sulfolane (0.94 mL) and o-DCB (2.50 mL) was added. The Schlenk flask was closed and inertised with argon. The mixture was stirred (400 rpm) and heated to 175° C. After 10 min at this temperature, a solution of TDI (1.0 g, 5.74 mmol), ISDGE (0.15 g, 0.56 mmol), BADGE (1.72 g, 5.06 mmol) and BPGE (0.05 g, 0.23 mmol) in o-DCB (2.82 mL) was added at a rate of 1 mL/min. After 60 min, para-tert-butylphenyl glycidyl ether (0.24 g, 1.15 mmol), dissolved in o-DCB (2.0 mL), was added to the reaction solution and stirred for 30 min. Subsequently 10 mL of N-methyl pyrrolidone was added to the reaction mixture, stirred for 10 min and then allowed to cool to room temperature.

[0170] The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm.sup.−1) in the IR spectrum from the reaction mixture. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was washed with MeOH three times and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 140° C. for 8 h and analysed.

[0171] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1749 cm.sup.−1.

[0172] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.−1 was not observed.

[0173] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0174] Thermogravimetric analysis of the product showed a mass loss of 0.2 wt % after tempering at 240° C. for 1 h and a mass loss of 0.2 wt % after tempering at 260° C. for 1 h.

TABLE-US-00001 TABLE 1 Comparison of the results of Examples 1 to 8. n(ISDGE)/ Com- Com- (n(ISDGE) + Com- Com- Com- pound pound n(BADGE) pound pound pound Addition T.sub.G T.sub.D Δwt Δwt Δwt Example (A) (B) [mol-%] (C) (D) (F) Protocol X(A) [° C.] [° C.] %.sup.240 %.sup.260 %.sup.280 1 TDI ISDGE 100 LiBr BPGE — 2 Complete 161.1 400.7 −0.6 −0.8 −1.3 2 TDI ISDGE 100 LiBr BPGE BPGE 2 Complete 162.3 394.4 −0.4 −0.5 −0.7 3 (comp.) TDI ISDGE 100 LiBr BPGE — 1 Incomplete n.d. 364.2 n.d. n.d. n.d. 4 (comp.) TDI ISDGE 100 Ph.sub.4PBr BPGE — 2 Complete 166.6 398.8 −0.8 −1.1 −1.7 5 (comp.) TDI ISDGE 100 LiBr — — 2 Complete 164.4 397.9 −0.8 −1.1 −1.6 6 TDI ISDGE/BADGE 50 LiBr BPGE BPGE 2 Complete 174.1 399.0 −0.2 −0.3 −0.6 7 TDI ISDGE/BADGE 20 LiBr BPGE BPGE 2 Complete 180.4 392.5 −0.2 −0.3 −0.6 8 TDI ISDGE/BADGE 10 LiBr BPGE BPGE 2 Complete 183.6 402.1 −0.2 −0.2 −0.5 comp.: comparative example, n.s.: not soluble, n.d. not determined Addition protocol 1: Solution of diisocyanate compound (A) is added to a solution of bisepoxide compound (B) and the catalyst (C) in a semi-batch process, the compound (D) is added in a second step according to example 14 in EP 16703330.7. Addition protocol 2: A solution of the diisocyanate compound (A), the bisepoxide compound (B) and the compound (D) is added to the reactor containing the catalyst (C) dissolved in the solvent (E) comprising the solvent (E-1) according to claim 1 of the present application. X(A): Conversion of isocyanates as compound (A) after step (β) estimated by IR spectroscopy of the reaction mixture. PDI Polydispersity index (PDI) defined as ratio of the weight average molecular weight and the number average molecular weight determined by GPC Δwt % weight loss percentage of the sample after treatment at 240° C., 260° C. and 280° C. for 1 h, respectively, with respect to the thermoplastic polyoxazolidinone (D) obtained in step (β), determined by TGA.