Anionic copolymerization of 2-pyrrolidone with caprolactam or piperidone

• US 4,101,531 A
• Filed: 04/25/1977
• Issued: 07/18/1978
• Est. Priority Date: 05/19/1976
• Status: Expired due to Term

• Current Assignee: Chevron Research Company (Chevron Corp.)
• Original Assignee: Chevron Research Company (Chevron Corp.)
• Inventors: Bacskai, Robert
• Primary Examiner(s): Anderson, Harold D.
• Application Number:
  US05/790,776
• Time in Patent Office: 449 Days
• Field of Search: 260/78 P, 260/78 L
• US Class Current: 528/315
• CPC Class Codes: C08G 69/24 Pyrrolidones or piperidones

Abstract

Copolymers of 2-pyrrolidone and C₅ -C₆ lactams (caprolactam and piperidone) are provided in solid form, at relatively high rates and molecular weights by polymerization in the presence of alkaline catalysts and carbon dioxide, by the inclusion of an auxiliary catalyst and a copolymerization promoter comprising certain onium salts and N-acyl lactams, respectively.

Claims

1. A process for the production of a solid copolymer of 2-pyrrolidone and a lactam having five or six carbon atoms in its ring, which comprises polymerizing a mixture of 2-pyrrolidone and said lactam by contacting the mixture with a catalyst system consisting essentially of an alkaline polymerization catalyst, and an auxiliary catalyst which is a quaternary Group VA onium salt, carbon dioxide and a copolymerization promoter.

2. The process according to claim 1 wherein said alkaline polymerization catalyst is potassium or sodium pyrrolidonate.

3. The process according to claim 1 wherein said alkaline polymerization catalyst is a lactamate salt of an alkali metal.

4. The process according to claim 3 wherein said lactamate salt of an alkali metal is a pyrrolidonate.

5. The process according to claim 4 wherein said pyrrolidonate is potassium pyrrolidonate.

6. The process according to claim 1 wherein said auxiliary catalyst is a quaternary ammonium of phosphonium salt.

7. The process according to claim 6 wherein said salt is a halide or carboxylate.

8. The process according to claim 7 wherein said halide is a chloride or bromide and said carboxylate is the alkanoate of a C₁ -C₆ alkanoic acid.

9. The process according to claim 1 wherein said auxiliary catalyst is a quaternary ammonium salt.

10. The process according to claim 9 wherein said ammonium salt is a tetraalkyl ammonium halide or carboxylate.

11. The process according to claim 9 wherein said ammonium salt is a tetraalkyl ammonium halide.

12. The process according to claim 10 wherein said salt is a tetra (C₁ -C₆) alkyl ammonium halide.

13. The process according to claim 11 wherein said halide is tetramethyl ammonium chloride.

14. The process according to claim 1 wherein said copolymerization promoter is an N-acyl lactam.

15. The process according to claim 14 wherein said N-acyl lactam is N-acyl pyrrolidone.

16. The process according to claim 1 wherein said copolymerization promoter is 1-(1-pyrrolin-2-yl)-2-pyrrolidone.

17. The process according to claim 1 wherein said promoter is acetic anhydride, or N-acetyl pyrrolidone.

23. The process of claim 1 wherein said polymerization is conducted at a temperature of at least 50°

C.

24. The process of claim 8 wherein said polymerization is conducted at a temperature of at least 50°

C.

25. The process of claim 24 wherein said lactam is caprolactam.

18. A process for the production of a solid copolymer of 2-pyrrolidone and a lactam, having five or six carbon atoms in its ring, which comprises contacting 2-pyrrolidone, said lactam, an alkali metal lactamate, a tetraalkyl ammonium halide, carbon dioxide and a N-acyl lactam to form a mixture, at a temperature of about 20°

-50°

C, and polymerizing said mixture at a temperature in excess of about 50°

C.

19. The process of claim 18 wherein said polymerization is carried out at a temperature greater than about 50°

and less than about 80°

C for a period of about 8-48 hours.

20. The process according to claim 18 wherein said N-acyl lactam is selected from the group consisting of N-acetyl pyrrolidone, pyrrolinyl-pyrrolidone and acetic anhydride.

21. A process for the production of a solid copolymer of 2-pyrrolidone with a lactam having five or six carbon atoms in its ring, which comprises reacting 2-pyrrolidone with less than a stochiometric amount of of a source of alkali metal, removing the water formed during the reaction to obtain an essentially anhydrous solution of alkali metal pyrrolidonate in 2-pyrrolidone, contacting the solution with carbon dioxide, and admixing with the solution said lactam, a tetraalkyl ammonium halide and a N-acyl lactam, and polymerizing the mixture at a temperature of at least 40°

C.

22. A process for the production of a solid copolymer of 2-pyrrolidone with lactam, having five or six carbon atoms in its ring, which comprises polymerizing a mixture of 2-pyrrolidone and a 2-pyrrolidone lactam by contacting the mixture with a catalyst system consisting essentially of an alkaline polymerization catalyst, a N-acyl lactam and an adduct of carbon dioxide and a lactam salt selected from the group consisting of a tetraalkyl ammonium salt of 2-pyrrolidone or lactams having five or six carbon atoms in their rings and mixtures thereof;

and mixtures of said tetraalkyl ammonium salt with an alkali metal salt of said lactam, and mixtures thereof.