SYNTHESIS OF LINEAR POLYOXAZOLIDINONES USING URETDIONES AS DIISOCYANATE COMPONENT

Abstract

A process for preparing a thermoplastic polymer involves reacting at least components (a) to (b), in the presence of a catalyst composition (c). Component (a) is an isocyanate composition containing at least one uretdione diisocyanate (a-i), and component (b) is an epoxide composition containing at least one diepoxide (b-i). The catalyst composition (c) contains at least one ionic liquid (c-i), preferably selected from 1-ethyl-3-methyl imidazolium bromide, 1-benzyl-3-methyl imidazolium chloride. 1-butyl-1-methylpiperidinium chloride, 1-ethyl-2,3-dimethylimidazolium bromide, 1-(2-hydroxyethyl)-3-methyl imidazolium chloride, butyl-1-methylpiperidinium acetate, or mixtures of two or more thereof. A thermoplastic polymer obtained or obtainable from the process is useful for the preparation of a fibre or a molded article or as a modifier for another thermoplastic material.

Claims

1: A process for preparing a thermoplastic polymer, comprising: reacting at least components (a) to (b): (a) an isocyanate composition comprising at least one uretdione diisocyanate (a-i); (b) an epoxide composition comprising at least one diepoxide (b-i); in the presence of a catalyst composition (c), wherein the catalyst composition (c) comprises at least one ionic liquid (c-i) selected from the group consisting of 1-ethyl-3-methyl imidazolium bromide (EMIM-Br), 1-benzyl-3-methyl imidazolium chloride (BEMIM-Cl), 1-butyl-1-methylpiperidinium chloride (BMPM-Cl), 1-ethyl-2,3-dimethylimidazolium bromide (EDMIM-Br), 1-(2-hydroxyethyl)-3-methyl imidazolium chloride (HEMIM-C1), butyl-1-methylpiperidinium acetate (BMPM acetate), and a mixture of two or more thereof.

2: The process of claim 1, wherein the at least one uretdione diisocyanate (a-i) has the formula (I) ##STR00009## wherein R.sup.1 and R.sup.2 are each independently selected from the group consisting of: branched and unbranched C1 to C10-alkylene group; substituted or unsubstituted C4 to C10-cycloalkyl group, wherein a substituted C4 to C10-cycloalkyl group has one or more substituents independently selected from branched or unbranched C1 to C5-alkyl group; C1 to C5 alkylene-bridged dicyclohexyl group; substituted or unsubstituted C6 to C10-aryl group, wherein a substituted C6 to C10-aryl group has one or more substituents independently selected from branched or unbranched C1 to C5-alkyl group; and C1 to C5-alkylene-bridged di-C6 to C10-aryl group, wherein each C6 to C10-aryl group is unsubstituted or substituted with one or more substituents independently selected from branched or unbranched C1 to C5-alkyl group; and wherein n and q are independently zero or 1, and m is zero or an integer in a range of from 1 to 10.

3: The process of claim 2, wherein the at least one uretdione diisocyanate (a-i) is selected from the group consisting of isophorone diisocyanate uretdione (IPDI-U), toluene diisocyanate uretdion (TDI-U), methylene diisocyanate uretdione (MDI-U), and a mixture of two or more thereof.

4: The process of claim 1, wherein i) the isocyanate composition (a) comprising at least one uretdione diisocyanate (a-i) is reacted with the epoxide composition kb) comprising at least one diepoxide (b-i), in the presence of flail the catalyst composition (c), thereby obtaining a reaction mixture; and ii) at least one monoisocyanate (ai-iii) with an NCO-functionality of 1 is added to the reaction mixture obtained in.

5: The process of claim 1, wherein at least 98 weight-% of the epoxide composition (b) consists of the at least one diepoxide (b-i), relative to an overall weight of the epoxide composition (b).

6: The process of claim 1, wherein the catalyst composition (c) comprises at least BMPM-Cl.

7: The process of claim 1, wherein reacting the isocyanate composition (a) and the epoxide composition (b) in the presence of the catalyst composition (c) is done at a temperature in a range of from 100 to 300° C.; and/or wherein reacting the isocyanate composition (a) and the epoxide composition, (b) in the presence of the catalyst composition (c) is done at a pressure in a range of from 900 to 1500 mbar.

8: The process of claim 4, wherein a molar ratio of the at least one diepoxide (b-i) to the at least one uretdione diisocyanate (a-i) is in a range of from 1.0:0.5 to 0.5:1.0; and/or wherein a molar ratio of the at least one uretdione diisocyanate (a-i) added in i) to the at least one monoisocyanate (ai-iii) added in ii) is in a range of from 99.9:0.02 to 99.8:0.04.

9: The process of claim 1, wherein a catalyst concentration is in a range of from 0.05 Mol-% to 5 Mol-%, relative to epoxide groups of the at least one diepoxide (b-i).

10: The process of claim 1, wherein the epoxide composition (h) and the catalyst composition (c) are initially mixed to obtain a pre-mixture (h+c), and wherein the isocyanate composition (a) is added to the pre-mixture (b+c).

11: The process of claim 1, wherein the process is a bulk process, or wherein reacting the isocyanate composition (a) and the epoxide composition (b) in the presence of the catalyst composition (c) is done in a solvent.

12: The thermoplastic polymer, obtained from the process according to claim 1.

13: A thermoplastic polymer, obtained from a reaction of at least: a) an isocyanate composition comprising at least one uretdione diisocyanate (a-i); b) an epoxide composition comprising at least one diepoxide (b-i); and in the presence of a catalyst composition (c).

14: A method, comprising: forming a fibre or molded article comprising the thermoplastic polymer obtained from the process according to claim 1, by injection molding, calendering, powder sintering, laser sintering, melt pressing, or extrusion.

15: The process of claim 3, wherein the at least one uretdione diisocyanate (a-i) comprises TID-U.

16: The process of claim 4, wherein the at least one monoisocyanate (ai-iii) is added in an amount in a range of from 0.01 to 0.5 mol-%, in relation to 100 mol-% of the at least one diepoxide (b-i).

17: The process of claim 4, wherein the at least one monoisocyanate (ai-iii) is selected from the group consisting of n-hexylisocyanate, cyclohexyl isocyanate, omega-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, dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoro methyl phenyl isocyanate, benzyl isocyanate, 2,6-dimethylphenylisocyanate, 3,4-dimethylphenylisocyanate, 3,6-dimethylphenylisocyanate, 4-dodecylphenylisocyanat, 4-cyclohexyl-phenyl isocyanate, 4-pentylphenyl isocyanate, 4-tert-butyl phenyl isocyanate, 1-naphthyl isocyanate, and a mixture of two or more thereof.

18: The process of claim 5, wherein the at least one diepoxide (b-i) comprises bisphenol-A-diglycidylether.

19: The process of claim 11, wherein the solvent comprises one or more polar aprotic solvents.

20: The process of claim 11, wherein the solvent is selected from the group consisting of 1,3-dimethyl-2-imidazolidinon (DMI); dichlorobenzene; 1, 2, 3-trichlorobenzene; 1,2,4-trichlorobenzene; 1,3,5-trichlorobenzene; sulfolane; mesitylene; N-methyl pyrrolidone; 4-formyl morpholine; tert-butyl pyrrolidin-2-on; N-butyl pyrrolidone; and a mixture of two or more thereof.

Description

DESCRIPTION OF FIGURES

[0146] FIG. 1: shows the DSC diagram from the TDI urethdione obtained from T100 (Reference Example 1).

[0147] FIG. 2: shows the DSC curves of TDI uretdione made from T80 (Reference Example 2). It can be seen that by passing the ring opening temperature of the uretdione (160° C., dark grey curve), TDI was released and the melting peaks of 2,4-TDI and 2,6-TDI were captured (light grey curve) proving that the uretdione consisted of both, 2,4-TDI and 2,6-TDI.

CITED LITERATURE

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