Synthesis of linear polyoxazolidinones using uretdiones as diisocyanate component

Patent metadata

Field	Value
Publication number	US-12509547-B2
Application number	US-202118006012-A
Country	US
Kind code	B2
Filing date	Jul 22, 2021
Priority date	Jul 23, 2020
Publication date	Dec 30, 2025
Grant date	Dec 30, 2025

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.

First claim

The invention claimed is:

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-Cl), 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)

wherein R 1 and R 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 uretdione (TDI-U), methylene diisocyanate uretdione (MDI-U), and a mixture of two or more thereof.

4 . The process of claim 3 , wherein the at least one uretdione diisocyanate (a-i) comprises toluene diisocyanate uretdione (TDI-U).

5 . 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 (b) comprising at least one diepoxide (b-i), in the presence of 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 i).

6 . The process of claim 5 , 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).

7 . The process of claim 5 , 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.

8 . 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).

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

10 . The process of claim 1 , wherein the catalyst composition (c) comprises at least 1-butyl-1-methylpiperidinium chloride (BMPM-Cl).

11 . 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.

12 . 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.

13 . 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).

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

15 . 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.

16 . The process of claim 15 , wherein the solvent comprises one or more polar aprotic solvents.

17 . The process of claim 15 , 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.

Assignees

• Basf Se

Inventors

• Quell Aggeliki
• Thomas Hans-Josef
• Eling Berend

Classifications

• C08G18/71

  Monoisocyanates or monoisothiocyanates · CPC title

• C08G18/2018

  having one nitrogen atom in the ring · CPC title

• C08G59/686

  containing nitrogen · CPC title

• C08G18/798

  containing urethdione groups · CPC title

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title