Initiator system for cationic polymerization of olefins

Patent metadata

Field	Value
Publication number	US-11168100-B2
Application number	US-201716771375-A
Country	US
Kind code	B2
Filing date	Dec 14, 2017
Priority date	Dec 14, 2017
Publication date	Nov 9, 2021
Grant date	Nov 9, 2021

Abstract

A Brønsted-Lowry acid initiator system for cationic polymerization of an ethylenically unsaturated monomer involves an initiator having a structure of Formula (I) in an anhydrous polymerization medium:where: M is tantalum (Ta), vanadium (V) or niobium (Nb); R1, R2, R3 and R4 are the same or different and are independently H, F, Cl, Br, I, alkyl or aryl, or two or more of R2, R3, R4 and R5 on a same benzene ring are taken together to form a bicyclic, tricyclic or tetracyclic moiety with the benzene ring, with the proviso that all of R1, R2, R3 and R4 on the same benzene ring are not H; L is absent or a molecule that coordinates to H+; and, x is 0 when L is absent, or x is 0.5 or more when L is present.

First claim

What is claimed is:

1. A Brønsted-Lowry acid initiator system for cationic polymerization of an ethylenically unsaturated monomer, the Brønsted-Lowry acid initiator system comprising an initiator having a structure of Formula (I) in an anhydrous polymerization medium:

where:
M is tantalum (Ta), vanadium (V) or niobium (Nb);
R 1 , R 2 , R 3 and R 4 are the same or different and are independently H, F, Cl, Br, I, alkyl or aryl, or two or more of R 2 , R 3 , R 4 and R 5 on a same benzene ring are taken together to form a bicyclic, tricyclic or tetracyclic moiety with the benzene ring, with the proviso that all of R 1 , R 2 , R 3 and R 4 on the same benzene ring are not H;
L is absent or a molecule that coordinates to H + ; and,
x is 0 when L is absent, or x is 0.5 or more when L is present.

2. The system according to claim 1 , wherein M is Ta.

3. The system according to claim 1 , wherein L is a stabilizing molecule for the H + having one or more lone pairs of electrons.

4. The system according to claim 3 , wherein L is a sterically-hindered molecule.

5. The system according to claim 1 , wherein L is an alkyl ether or a cycloalkyl ether.

6. The system according to claim 1 , wherein L is diethyl ether.

7. The system according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are the same and are F or Cl.

8. The system according to claim 1 , wherein: M is Ta; R 1 , R 2 , R 3 and R 4 are Cl; L is Et 2 O; and, x is 2.

9. The system according to claim 1 , wherein the anhydrous polymerization medium comprises dichloromethane or methyl chloride.

10. The system according to claim 1 , containing substantially no water.

11. A process for producing a polymer, the process comprising polymerizing one or more ethylenically unsaturated monomers with the initiator system as defined in claim 1 .

12. The process according to claim 11 , wherein the polymerization is performed at a temperature of −85° C. or higher.

13. The process of claim 11 , wherein M is Ta.

14. The process of claim 11 , wherein L is a stabilizing molecule for the H + having one or more lone pairs of electrons.

15. The process of claim 14 , wherein L is a sterically-hindered molecule.

16. The process of claim 11 , wherein L is an alkyl ether or a cycloalkyl ether.

17. The process of claim 11 , wherein
i. L is diethyl ether; or
ii. the anhydrous polymerization medium comprises dichloromethane or methyl chloride; or
iii. the initiator system contains substantially no water.

18. The process of claim 11 , wherein R 1 , R 2 , R 3 and R 4 are the same and are F or Cl.

19. The process of claim 11 , wherein: M is Ta; R 1 , R 2 , R 3 and R 4 are Cl; L is Et 2 O; and, x is 2.

Assignees

• Arlanxeo Canada Inc
• Univ British Columbia
• Arlanxeo Singapore Pte Ltd

Inventors

• Arsenault Gilles
• Khatera Hazin
• Gates Derek

Classifications

• C07F9/00

  Compounds containing elements of Groups 5 or 15 of the Periodic Table · CPC title

• C08F112/12

  Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical · CPC title

• C08F4/20 Primary

  of antimony, bismuth, vanadium, niobium or tantalum · CPC title

• C08F116/18

  Acyclic compounds · CPC title

• C07C2/32 Primary

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title