Method for the production of thermoplastic polyoxazolidinone polymers

Patent metadata

Field	Value
Publication number	US-11299577-B2
Application number	US-201816642147-A
Country	US
Kind code	B2
Filing date	Sep 11, 2018
Priority date	Sep 15, 2017
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

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 (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.

First claim

The invention claimed is:

1. 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 comprising a polar aprotic solvent, wherein
the catalyst comprises an alkali halogenide, an earth alkali halogenide, or a transition metal halogenide, and wherein
the process comprises:
(a) placing the polar aprotic solvent and the catalyst in a reactor to provide a mixture,
(b) adding the diisocyanate compound, the bisepoxide compound and the chain regulator to the mixture resulting from step (a) to form a thermoplastic polyoxazolidinone, and
(c) reacting the thermoplastic polyoxazolidinone with an alkylene oxide,
wherein a calculated weight ratio of the sum of the weight of diisocyanate compound, bisepoxide compound, and chain regulator used to the sum of the weight of diisocyanate compound, bisepoxide compound, chain regulator, and polar aprotic solvent used in step (a) is from 5 wt % to 26 wt %.

2. The process according to claim 1 , wherein, in step (b), the the diisocyanate compound, the bisepoxide compound, and the chain regulator 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 the diisocyanate compound, the bisepoxide compound, and the chain regulator are added in a step-wise manner to the mixture resulting from step (a).

4. The process according to claim 1 , wherein the catalyst comprises LiCl, LiBr, LiI, MgCl 2 , MgBr 2 , MgI 2 , SmI 3 , or a combination of two or more thereof.

5. The process according to claim 1 , wherein the at least one of a monofunctional epoxide and monofunctional isocyanate 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-, or para-tolyl isocyanate, a 2,3,4 isomer of chlorophenyl isocyanate, dichlorophenyl isocyanate, 4-nitrophenyl isocyanate, 3-trifluoromethylphenyl isocyanate, benzyl isocyanate, dimethylphenylisocyanate, dodecylphenylisocyanate, 4-cyclohexyl-phenyl isocyanate, 4-pentyl-phenyl isocyanate, 4-t-butyl phenyl isocyanate, 1-naphthyl isocyanate, or a combination of two or more thereof.

6. The process according to claim 1 , wherein the polar aprotic solvent comprises sulfolane, dimethylsulfoxide, gamma-butyrolactone, or a combination of two or more thereof.

7. The process according claim 1 , wherein the alkylene oxide comprises a monofunctional alkylene oxide and/or a polyfunctional alkylene oxide.

8. The process according to claim 7 , 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.

9. The process of claim 1 , wherein the solvent composition comprises dichlorobenzene and sulfolane.

10. The process of claim 1 , wherein steps (a) and (b) are performed at a reaction temperature of ≥130° C. to ≤280° C. and a reaction time of 1 hour to 6 hours.

11. The process of claim 1 , wherein the calculated weight ratio of the sum of the weight of diisocyanate compound, bisepoxide compound, and chain regulator used to the sum of the weight of diisocyanate compound, bisepoxide compound, chain regulator, and polar aprotic solvent used in step (a) is from 8 wt-% to 26 wt-%.

12. The process of claim 1 , wherein the calculated weight ratio of the sum of the weight of diisocyanate compound, bisepoxide compound, and chain regulator used to the sum of the weight of diisocyanate compound, bisepoxide compound, chain regulator, and polar aprotic solvent used in step (a) is from 13 wt-% to 24 wt-%.

13. A thermoplastic polyoxazolidinone obtained by a process according to claim 1 .

14. A thermoplastic polyoxazolidinone according to claim 13 with a number average molecular weight Mn from ≥500 to ≤500,000 g/mol as determined with gel permeation chromatography (GPC).

15. A process for producing a thermoplastic polyoxazolidinone 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 comprising a polar aprotic solvent, wherein
the catalyst comprises an alkali halogenide, an earth alkali halogenide, or a transition metal halogenide, and wherein
the process comprises:
(a) placing the polar aprotic solvent and the catalyst in a reactor to provide a mixture,
(b) adding the diisocyanate compound, the bisepoxide compound and the chain regulator to the mixture resulting from step (a) to form a thermoplastic polyoxazolidinone, and
(c) reacting the thermoplastic polyoxazolidinone with an alkylene oxide,
wherein a calculated weight ratio of the sum of the weight of diisocyanate compound, bisepoxide compound, and chain regulator used to the sum of the weight of diisocyanate compound, bisepoxide compound, chain regulator, and polar aprotic solvent used in step (a) is from 5 wt % to 26 wt %,
wherein steps (a) and (b) are performed at a reaction temperat

Assignees

• Covestro Deutschland Ag

Inventors

• Koopmans Carsten
• Guertler Christoph
• Wolf Aurel
• Frick-Delaittre Elena
• Laemmerhold Kai
• Rangheard Claudine
• Breuer Timo

Classifications

• C08G18/831

  by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides (by aldehydes C08G18/84, by peroxides C08G18/86) · CPC title

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/003 Primary

  with epoxy compounds having no active hydrogen (with epoxy resins containing active hydrogen C08G18/58) · CPC title

• C08G18/0852

  the solvents being organic · CPC title

• C08G18/225 Primary

  of alkali or alkaline earth metals · CPC title