High molecular weight polyisobutylenes and polyisobutylene networks from liquid polyisobutylenes by thiol-ene clicking

Patent metadata

Field	Value
Publication number	US-11142596-B2
Application number	US-201916298225-A
Country	US
Kind code	B2
Filing date	Mar 11, 2019
Priority date	Mar 11, 2019
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

A polyisobutylene-based polymer network comprising the thiol-ene reaction product of at least two thiol-terminated polyisobutylene precursor polymers and at least one multi-functional allyl-containing precursor moiety or polymer in the presence of light or heat. The at least two thiol-terminated polyisobutylene precursor polymers have at least two thiol end groups. When each polyisobutylene precursor polymer has only two thiol end groups then the allyl-containing precursor moiety or polymer has at least three functional groups, and wherein when the allyl-containing precursor moiety or polymer has two functional groups then each polyisobutylene precursor polymer has at least three thiol end groups.

First claim

What is claimed is:

1. A polyisobutylene-based polymer network comprising the thiol-ene reaction product of:
at least two thiol-terminated polyisobutylene precursor polymers, each polyisobutylene precursor polymer having at least two thiol end groups; and
at least one multi-functional allyl-containing precursor moiety or polymer, in the presence of light or heat;
wherein when each polyisobutylene precursor polymer has only two thiol end groups then the allyl-containing precursor moiety or polymer has at least three functional groups, and wherein when the allyl-containing precursor moiety or polymer has two functional groups then each polyisobutylene precursor polymer has at least three thiol end groups.

2. The polyisobutylene-based polymer network of claim 1 wherein each polyisobutylene precursor polymer comprises a core and at least two polyisobutylene chains extending from the core, wherein each of the at least two polyisobutylene chains have a thiol end group.

3. The polyisobutylene-based polymer network of claim 1 , wherein each polyisobutylene precursor polymer has a formula selected from:

wherein m and m′ are each an integer from 2 to 5,000, and when present, m″ is an integer from 2 to 5,000.

4. The polyisobutylene-based polymer network of claim 1 , wherein the at least one multi-functional allyl-containing precursor moiety or polymer has a formula selected from:

wherein A represents an allyl group, M is a moiety and P is polymer.

5. The polyisobutylene-based polymer network of claim 4 wherein the at least one multi-functional allyl-containing precursor moiety is an

moiety represented by the specific formula

6. The polyisobutylene-based polymer network of claim 4 wherein the polymer is polyisobutylene.

7. A polyisobutylene-based polymer network comprising at least two sulfur containing polyisobutylene polymer segments and at least one residue of an allyl-containing moiety or polymer, wherein the at least two sulfur containing polyisobutylene polymer segments each include a core and at least two polyisobutylene polymer chains extending therefrom and including at least one sulfur atom being attached to the residue of the allyl-containing moiety or polymer, the residue of the allyl-containing moiety or polymer connecting the at least two sulfur containing polyisobutylene polymer segments together.

8. The polyisobutylene-based polymer network of claim 7 having the formula:

wherein n, n′, n″, and n′″ are each an integer from 2 to 5,000 and wherein each represents a polyisobutylene chain.

9. A method for creating a polyisobutylene-based polymer network, the method comprising:
providing at least two thiol-terminated polyisobutylene precursor polymers, each polyisobutylene precursor polymer having at least two thiol end groups;
adding at least one multi-functional allyl-containing precursor moiety or polymer with the at least two polyisobutylene precursor polymers to form a mixture;
wherein when each polyisobutylene precursor polymer has only two thiol end groups then the allyl-containing precursor moiety or polymer has at least three functional groups, and wherein when the allyl-containing precursor moiety or polymer has two functional groups then each polyisobutylene precursor polymer has at least three thiol end groups; and
irradiating the mixture with light or heating the mixture, so as to provide a thiol-ene reaction, thereby producing the polyisobutylene-based polymer network.

10. The method of claim 9 , wherein each polyisobutylene precursor polymer comprises an initiator core and at least two polyisobutylene chains extending from the initiator core, wherein each of the at least two polyisobutylene chains have a thiol end group.

11. The method of claim 9 , wherein each polyisobutylene precursor polymer has a formula selected from:

wherein m and m′ are each an integer from 2 to 5,000, and when present, m″ is an integer from 2 to 5,000.

12. The method of claim 9 , wherein the at least one multi-functional allyl-containing precursor moiety or polymer is selected from a formula selected from:

wherein A represents an allyl group, M is a moiety and P is polymer.

13. The method of claim 12 wherein the at least one multi-functional allyl-containing precursor moiety is an

moiety represented by the specific formula

14. The method of claim 12 wherein the polymer is polyisobutylene.

15. The method of claim 9 , wherein the step of irradiating includes heating the mixture in the presence of a free radical initiator to produce the polymer network.

Assignees

• Kennedy Joseph
• Nugay Turgut
• Nugay Nihan
• Univ Akron

Inventors

• Kennedy Joseph
• Nugay Turgut
• Nugay Nihan

Classifications

• C08F2/50

  with sensitising agents · CPC title

• C08K5/3492

  Triazines · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C08F210/10 Primary

  Isobutene · CPC title

• C08F8/34 Primary

  Introducing sulfur atoms or sulfur-containing groups · CPC title