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 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 () 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 () to the mixture resulting from the step (). The invention is also related to the resulting thermoplastic polyoxazolidinone.

Claims

1. A process for producing thermoplastic polyoxazolidinones comprising copolymerization of a diisocyanate compound with a bisepoxide compound in the presence of a catalyst and a compound comprising a mono-epoxide group, a mono-isocyanate group, or both in a solvent, wherein the catalyst comprises an alkali halogenide, an earth alkali halogenide, or a transition metal halogenide, , and wherein the process comprises the following steps: (a) placing the solvent and the catalyst in a reactor to provide a mixture, and (b) adding the diisocyanate compound, the bisepoxide compound and the compound comprising a mono-epoxide group, a mono-isocyanate group, or both to the mixture resulting from step (a).

2. The process according to claim 1, wherein, in step (b), the diisocyanate compound, the bisepoxide compound, and the compound comprising a mono-epoxide group, a mono-isocyanate group, or both, are added in a continuous manner to the mixture resulting from step (a).

3. The process according to claim 1, wherein, in step (b), the diisocyanate compound, the bisepoxide compound, and the compound comprising a mono-epoxide group, a mono-isocyanate group, or both, are added in a step-wise manner to the mixture resulting from step (a).

4. The process according to claim 1, wherein the diisocyanate compound-, the bisepoxide compound, and the compound comprising a mono-epoxide group, a mono-isocyanate group, or both, are mixed prior the addition to the mixture resulting from step (a).

5. The process according to claim 4, wherein, in step (b), the mixture of the diisocyanate compound, the bisepoxide compound, and the compound comprising a mono-epoxide group, a mono-isocyanate group, or both, are added in a continuous manner to the mixture resulting from step (a).

6. The process according to claim 4, wherein, in step (b), the mixture of the diisocyanate compound, the bisepoxide compound, and the compound comprising a mono-epoxide group, a mono-isocyanate group, or both, are added in a step-wise manner with two or more individual addition steps to the mixture resulting from step (a).

7. The process according to claim 1, wherein the solvent comprises 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 combination of two or more thereof.

9. The process according to claim 1, wherein the compound comprising a mono-epoxide group, a mono-isocyanate group, or both 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, -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-, or para-tolyl isocyanate, a 2,3,4 isomer of chlorophenyl isocyanate, dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenylisocyanate, dodecylphenylisocyanat, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-t-butyl phenyl isocyanate, 1-naphthyl isocyanate, or a combination of two or more thereof.

10. The process according to any one of claim 7, wherein the polar aprotic solvent comprises sulfolane, dimethylsulfoxide, gamma-butyrolactone, or a combination of two or more thereof.

11. A process for the production of a thermoplastic polyoxazolidinone, comprising reacting the polyoxazolidinone of claim 1 with an alkylene oxide.

12. The process according claim 11, wherein the alkylene oxide comprises a monofunctional alkylene oxide and/or a polyfunctional alkylene oxide.

13. The process according to claim 12, wherein the alkylene oxide comprises a monofunctional alkylene oxide comprising 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 combination of any two or more thereof.

14. A thermoplastic polyoxazolidinone (O) obtained by a process according to claim 11.

15. A thermoplastic polyoxazolidinone (O) according to claim 14 with a number average molecular weight Mn from 500 to 500,000 g/mol, as determined with gel permeation chromatography (GPC).

Description

EXAMPLES

[0104] The present invention will be further described with reference to the following examples without wishing to be limited by them.

Diisocyanate Compound (A)

[0105] A-1: Methylene diphenyl diisocyanate (MDI), 98%, Covestro AG, Germany [0106] A-2: 2,4-Toluenediisoyanate >99% (TDI) 2,4-Isomer, Covestro AG, Germany

Epoxide Compound (B)

[0107] B-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.

Catalyst (C)

[0108] C-1: LiCl Lithium chloride, purity >99%, was obtained from Sigma Aldrich [0109] C-2: LiBr Lithium bromide, purity >99,995%, was obtained from Sigma Aldrich [0110] C-3: Ph3P(PhOMe)Br triphenyl-o-methoxyphenyl phosphonium bromide was synthesized and purified as described in the literature (Adv. Synth. Catal. 2008, 350, 2967-2974)

Solvents (E)

[0111] Ortho-dichlorobenzene (o-DCB), purity 99%, anhydrous, was obtained from Sigma-Aldrich, Germany

[0112] N-Methylpyrrolidone (NMP), purity 99.5%, anhydrous, was obtained from Sigma-Aldrich, Germany.

Sulphur Containing Solvent (E-1)

[0113] Sulfolane, purity 99%, anhydrous, was obtained from Sigma-Aldrich, Germany

Compound (D) and (F)

[0114] BPGE para-tert.-butylphenylglycidylether (94%, Denacol EX-146, Nagase Chem Tex Corporation, Japan) [0115] PTI p-tolylisocyanate: purity 99%, anhydrous, was obtained from Sigma-Aldrich, Germany

[0116] TDI, MDI, LiCl, LiBr were used as received without further purification. BADGE (Epikote 162) and sulfolane was used after melting at 50 C. and drying over molecular sieves. o-DCB and NMP were dried over molecular sieves prior to use. BPGE and PTI were distilled prior to use

[0117] 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.

[0118] Addition protocol 2: 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.

Characterisation of Polyoxazolidinone

IR

[0119] 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

[0120] 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

[0121] The average chain length of the thermoplastic polyoxazolidinones was controlled by the molar ratio of diepoxide, diisocyanate and/or compound (D).

[0122] 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) [0123] with q=n.sub.x/n.sub.y1 and x,y=bisepoxide (B) or diisocyanate (A) [0124] and with the conversion p

[0125] 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 25 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 four 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 midpoint of the intersection point between the tangent at low temperature and the tangent in the mid temperature range and the intersection point between the tangent in the mid temperature range and the tangent at high temperature is stated. The reported T.sub.g was 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.sup.e SW 11.00 was used. The sample (6 to 20 mg) was weighed in a 70 L 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 (35 mL/min) and the relative weight loss was followed in dependence of temperature. For data analysis the software STAR.sup.e 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 70 L Alox pan (previously cleaned at 1000 C. for 7 hrs), heated from 25 C. to the target temperature (240 C. and 260 C. respectively) with a heating rate of 10 K/min under argon flow (35 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 wt %.sup.T given in the examples is the weight loss percentage of the sample after 1 h at the target temperature T.

GPC

[0128] GPC measurements were performed at 40 C. in N,N-dimethylacetamide (DMAc, flow rate of 0.675 mL min.sup.1). The column set consisted of 4 consecutive columns (GRAM precolumn, GRAM 3000, GRAM 3000, GRAM 100). Samples (concentration 2-3 g L.sup.1, injection volume 20 L) were injected employing an Agilent technologies 1260 Infinity auto sampler. An RID detector was used to follow the concentration at the exit of the column. Raw data were processed using the PSS WinGPC Unity software package. Polystyrene of known molecular weight was used as reference to calculate the molecular weight distribution. The number average molecular weight measured by GPC is denominated as M.sub.n(GPC) in the examples.

Reactor

[0129] The 300 ml stainless steel PARR reactor used in the examples had a height (internal) of 10.16 cm and an internal diameter of 6.35 cm. The reactor was fitted with an electric heating jacket (510 watt maximum heating capacity). The reactor is equipped with a counter cooling consisted of a U-shaped dip tube of external diameter 6 mm which projected into the reactor to within 5 mm of the bottom. The reactor was also fitted with an inlet tube and a temperature probe of diameter 1.6 mm, both of which projected into the reactor to within 3 mm of the bottom. A machined spiral stirrer from PARR was used in the examples. An HPLC pump (KNAUER smartline pump 100 with pressure sensor) was connected to the reactor to add solution during the reaction.

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

[0130] A reactor as previously described was charged with LiBr (0.16 g, 1.84 mmol). Then sulfolane (15 mL) and oDCB (40 mL) was added. The reactor 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 (16.00 g, 91.87 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0,754 g, 3.62 mmol) in oDCB (45 mL) was added at a rate of 1 mL/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0131] 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.

[0132] The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0133] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1749 cm.sup.1.

[0134] In the solid state IR spectrum the characteristic signal for isocyanurate groups was not observed.

[0135] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0136] Thermogravimetric analysis of the product showed a mass loss of 0.24 wt % after tempering at 240 C. for 1 h and a mass loss of 0.52 wt % after tempering at 260 C. for 1 h.

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

[0137] A reactor as previously described was charged with LiCl (0.08 g, 1.84 mmol). Then sulfolane (15 mL) and oDCB (40 mL) were added. The reactor 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 (16.00 g, 91.87 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0.75 g, 3.62 mmol) in oDCB (45 mL) was added at a rate of 1 mL/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0138] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0139] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm.sup.1.

[0140] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was not observed.

[0141] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0142] Thermogravimetric analysis of the product showed a mass loss of 0.32 wt % after tempering at 240 C. for 1 h and a mass loss of 0.37 wt % after tempering at 260 C. for 1 h.

Example 3: Polymerization of TDI as Compound (A) and BADGE as (B) with BPGE as Compound (D) Using LiCl as Compound (C) with Addition Protocol 2 without Sulfolane as Solvent (E-1)

[0143] A reactor as previously described was charged with LiCl (0.08 g, 1.84 mmol). Then oDCB (55 mL) was added. The reactor 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 (16.00 g, 91.87 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0.75 g, 3.62 mmol) in oDCB (45 mL) was added at a rate of 1 mL/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0144] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0145] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm.sup.1.

[0146] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm.sup.1 was observed.

[0147] 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 BADGE as Compound (B) with BPGE as (Compound (D) Using LiBr as Compound (C) with Addition Protocol 1 with Sulfolane as Solvent (E-1)

[0148] A reactor as previously described was charged with LiBr (0.16 g, 1.84 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0.75 g, 3.62 mmol). Then sulfolane (10 mL) and oDCB (25 mL) were added. The reactor 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 (16 g, 91.87 mmol) in oDCB (50 mL) was added at a rate of 1 mL/min. After 120 min, the stirring stopped due to gelification in the reactor.

[0149] Analysis of the reaction mixture by IR spectroscopy showed uncomplete conversion of the isocyanate groups (2260 cm-1).

[0150] The polymer was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The polymer was twice resuspended in methanol, stirred 24 h and filtered.

[0151] The polymer was then dried under vacuum at 150 C. for 6 h and analysed.

[0152] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group at 1749 cm.sup.1 was not observed.

[0153] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was observed.

[0154] The polymer obtained was not soluble in NMR solvent.

Example 5 (Comparison): Polymerization of TDI as Compound (A) and BADGE as Compound (B) with BPGE as Compound (d) Using Ph.SUB.3.P(PhOMe)Br as Compound (c) with Addition Protocol 2 with Sulfolane as Solvent (E-1)

[0155] A reactor as previously described was charged with Ph.sub.3P(PhOMe)Br (0.83 g, 1.84 mmol). Then sulfolane (15 mL) and oDCB (40 mL) was added. The reactor 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 (16.00 g, 91.87 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0,754 g, 3.62 mmol) in oDCB (45 mL) was added at a rate of 1 m/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0156] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0157] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1749 cm.sup.1.

[0158] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was not observed.

[0159] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0160] Thermogravimetric analysis of the product showed a mass loss of 0.56 wt % after tempering at 240 C. for 1 h and a mass loss of 0.82 wt % after tempering at 260 C. for 1 h.

Example 6 (Comparison): Polymerization of TDI as Compound (A) and BADGE as Compound (B) with BPGE as Compound (D) Using Ph.SUB.3.P(PhOMe)Br as Compound (C) with Addition Protocol 2 without Sulfolane as Solvent (E-1)

[0161] A reactor as previously described was charged with Ph.sub.3P(PhOMe)Br (0.83 g, 1.84 mmol). Then oDCB (55 mL) was added. The reactor 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 (16.00 g, 91.87 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0.75 g, 3.62 mmol) in oDCB (45 mL) was added at a rate of 1 mL/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0162] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0163] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1749 cm.sup.1.

[0164] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was not observed.

[0165] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0166] Thermogravimetric analysis of the product showed a mass loss of 0.41 wt % after tempering at 240 C. for 1 h and a mass loss of 0.76 wt % after tempering at 260 C. for 1 h.

Example 7 (Comparison): Polymerization of TDI as Compound (A) and BADGE as Compound (B) with BPGE as Compound (D) Using Ph.SUB.3.P(PhOMe)Br as Compound (C) with Addition Protocol 1 without Sulfolane as Solvent (E-1)

[0167] A reactor as previously described was charged with Ph.sub.3P(PhOMe)Br (0.83 g, 1.84 mmol), BADGE (30.66 g, 90.06 mmol) and BPGE (0.75 g, 3.62 mmol). Then oDCB (25 mL) were added. The reactor 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 (16 g, 91.87 mmol) in oDCB (70 mL) was added at a rate of 1 mL/min. After 420 min, 50 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0168] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0169] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm.sup.1.

[0170] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was observed.

[0171] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0172] Thermogravimetric analysis of the product showed a mass loss of 1.40 wt % after tempering at 240 C. for 1 h and a mass loss of 1.86 wt % after tempering at 260 C. for 1 h.

Example 8 (Comparison): Polymerization of TDI as Compound (A) and BADGE as Compound (B) without Compound (D) Using LiCl as Compound (C) with Addition Protocol 2 with Sulfolane as Solvent (E-1)

[0173] A reactor as previously described was charged with LiCl (0.08 g, 1.84 mmol). Then sulfolane (15 mL) and oDCB (40 mL) were added. The reactor 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 (16.00 g, 91.87 mmol) and BADGE (30.66 g, 90.06 mmol) in oDCB (45 mL) was added at a rate of 1 mL/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0174] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0175] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm.sup.1.

[0176] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was not observed.

[0177] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0178] Thermogravimetric analysis of the product showed a mass loss of 0.71 wt % after tempering at 240 C. for 1 h and a mass loss of 0.74 wt % after tempering at 260 C. for 1 h.

Example 9: Polymerization of TDI as Compound (A) and BADGE as Compound (B) with p-Tolyl Isocyanate as Compound (D) Using LiCl as Compound (C) with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0179] A reactor as previously described was charged with LiCl (0.08 g, 1.84 mmol). Then sulfolane (15 mL) and oDCB (40 mL) were added. The reactor 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 (15.69 g, 90.06 mmol), BADGE (31.28 g, 91.87 mmol) and PTI (0.48 g, 3.62 mmol) in oDCB (45 mL) was added at a rate of 1 mL/min. After 210 min, 55 mL of NMP were added. After another 15 min, the reaction mixture was allowed to cool to room temperature.

[0180] 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. The thermoplastic polyoxazolidinone was precipitated in methanol, milled with an ultraturrax dispersing instrument and collected by filtration. The thermoplastic polyoxazolidinone was twice resuspended in methanol, stirred 24 h and filtered. The thermoplastic polyoxazolidinone was then dried under vacuum at 150 C. for 6 h and analysed.

[0181] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1747 cm.sup.1.

[0182] In the solid state IR spectrum the characteristic signal for isocyanurate groups at 1710 cm-1 was not observed.

[0183] In the .sup.1H NMR spectrum, the characteristic methine and methylene signals assigned to the oxazolidinone moieties were observed.

[0184] Thermogravimetric analysis of the product showed a mass loss of 0.35 wt % after tempering at 240 C. for 1 h and a mass loss of 0.63 wt % after tempering at 260 C. for 1 h.

Example 10: Polymerization of MDI as Compound (A) and BADGE as Compound (B) Using a Low Monomer Concentration and LiCl as Catalyst (C) and Para-Tert-Butylphenyl Glycidyl Ether as Compound (D) and Addition of a Compound (F) Added in a Second Step with Addition Protocol 2 and Sulfolane as Solvent (E-1)

[0185] Under a continuous flow of nitrogen, a glass flask (500 mL) was charged with LiCl (0.0999 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 (0.9724 g), bisphenol A glycidyl ether (39.3150 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 (4.862 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 60 min. The completion of the reaction was confirmed by the absence of the isocyanate band (2260 cm-1) in the IR spectrum. 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.

[0186] Thermogravimetric analysis of the product (tempering at 260 C. for 1 h and at 280 C. for 1 h) showed mass loss of 0.11 wt. % and 0.16 wt. %, respectively.

[0187] In the solid state IR spectrum the characteristic signal for the oxazolidinone carbonyl group was observed at 1750 cm-1.

Comparison

[0188]

TABLE-US-00001 TABLE 1 Comparison of the results of Examples to 10. Addi- Com- Com- Com- Com- tion pound pound pound pound Proto- Solvent Mn T.sub.G T.sub.D Example (A) (C) (D) (F) col (E-1) X(A) [g/mol] PDI [ C.] [ C.] wt %.sup.240 wt %.sup.260 1 TDI LiBr BPGE 2 Sulfolane Complete 14284 2.4 183.2 400.9 0.24 0.52 2 TDI LiCl BPGE 2 Sulfolane Complete 12618 3.9 180.7 390.1 0.32 0.37 3 TDI LiCl BPGE 2 Complete 6222 2.7 183.2 272.0 1.50 1.53 (comp.) 4 TDI LiBr BPGE 1 Sulfolane Incom- n.s. n.s. 161.6 252.3 n.d. n.d. (comp.) plete 5 TDI Ph.sub.3P(PhOMe)Br BPGE 2 Sulfolane Complete 9055 3.2 188.2 390.2 0.56 0.82 (comp.) 6 TDI Ph.sub.3P(PhOMe)Br BPGE 2 Complete 9830 4.7 185.1 384.2 0.41 0.76 (comp.) 7 TDI Ph.sub.3P(PhOMe)Br BPGE 1 Complete 7902 4.7 170.7 395.3 1.40 1.86 (comp.) 8 TDI LiCl 2 Sulfolane Complete 12906 13.1 194.9 390.6 0.71 0.74 (comp.) 9 TDI LiCl PTI 2 Sulfolane Complete 13138 3.6 187.9 391.65 0.35 0.63 10 MDI LiCl BPGE BPGE 2 Sulfolane Complete 11220 5.07 175.3 345 n.d. 0.11 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 () 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 wt % weight loss percentage of the sample after treatment at 240 C. and 260 C. for 1 h, respectively, with respect to the thermoplastic polyoxazolidinone (D) obtained in step (), determined by TGA.