Preparation of polyisobutylene-based polymer networks by thiol-ene chemistry

Patent metadata

Field	Value
Publication number	US-9975971-B2
Application number	US-201414769709-A
Country	US
Kind code	B2
Filing date	Mar 4, 2014
Priority date	Mar 4, 2013
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

A PIB-based polymer network includes at least one sulfur containing segment and at least two PIB polymer segments. The at least two PIB polymer segments each include a core and at least two polyisobutylene polymer chains extending therefrom. The at least one sulfur containing segment includes at least one sulfur atom that is located between any two polyisobutylene polymer chains from two different PIB polymer segments, so that the sulfur containing segment connects those two different PIB polymer segments together. The PIB-based polymer network is produced by the thiol-ene reaction in the presence of light or heat. The reaction products include at least two polyisobutylene polymer precursor moieties, each polyisobutylene polymer precursor moiety having at least two end group selected from the end groups —CH 2 —CH(CH 3 )═CH 2 , —CH 2 ═C(CH 3 ) 2 , and —CH 2 —CH═CH 2 ; and at least one multi-functional thiol.

First claim

What is claimed is:

1. A polyisobutylene-based polymer network comprising the thiol-ene reaction product of:
at least two telechelic multi-functional polyisobutylene polymer precursor moieties, each telechelic multi-functional polyisobutylene polymer precursor moiety having at least two end group selected from the end groups —CH 2 —C(CH 3 )═CH 2 , —CH═C(CH 3 ) 2 , and —CH 2 — CH═CH 2 , and
at least one multi-functional thiol having a sulfur atom and at least two functional groups, in the presence of light or heat;
wherein when each telechelic multi-functional polyisobutylene polymer precursor moiety has two end groups, then the at least one multi-functional thiol has three or more functional groups, and wherein when the at least one multi-functional thiol has two functional groups, then each telechelic multi-functional polyisobutylene polymer precursor moiety has three or more end groups; and
wherein the at least one multi-functional thiol is selected from the formulas:
H—S—H,

HS CH 2 n —SH

wherein n is an integer from 1 to 12,

2. The polyisobutylene-based polymer network of claim 1 wherein each telechelic multi-functional polyisobutylene polymer precursor moiety comprises a core and at least two polyisobutylene chains extending from the core, wherein each of the at least two polyisobutylene chains have an end group selected from the end groups —CH 2 —C(CH 3 )═CH 2 , —CH═C(CH 3 ) 2 , and —CH 2 —CH═CH 2 .

3. The polyisobutylene-based polymer network of claim 2 , wherein the core is an aromatic initiator core.

4. The polyisobutylene-based polymer network of claim 3 , wherein said initiator core is formed from dimethyl-5-tert-butyl-1,3-benzyl dicarboxylate.

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

wherein m and m′ are each an integer from 2 to 5,000.

6. The polyisobutylene-based polymer network of claim 2 , wherein each polyisobutylene polymer precursor moiety comprises at least three polyisobutylene chains extending from a core, wherein each of the at least three polyisobutylene chains have an end group selected from the end groups —CH 2 —C(CH 3 )═CH 2 , —CH═C(CH 3 ) 2 , and —CH 2 —CH═CH 2 .

7. The polyisobutylene-based polymer network of claim 6 , wherein each polyisobutylene polymer precursor moiety has a formula selected from:

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

8. A PIB-based polymer network comprising at least one sulfur containing segment and at least two PIB polymer segments, wherein the at least two PIB polymer segments each include a core and at least two polyisobutylene polymer chains extending therefrom, the at least one sulfur containing segment includes at least two sulfur atoms that are located between any two polyisobutylene polymer chains from two different PIB polymer segments, the sulfur containing segment connecting those two different PIB polymer segments together; and wherein the PIB-based polymer network has a formula selected from:

wherein m, m′, and X are each an integer from 2 to 5,000 and n is an integer from 1 to 12.

9. A PIB-based polymer network comprising at least one sulfur containing segment and at least two PIB polymer segments, wherein the at least two PIB polymer segments each include a core and at least two polyisobutylene polymer chains extending therefrom, the at least one sulfur containing segment includes only one sulfur atom that is located between any two polyisobutylene polymer chains from two different PIB polymer segments, the sulfur containing segment connecting those two different PIB polymer segments together; and wherein the PIB-based polymer network having a formula selected from:

wherein m, m′, and X are each an integer from 2 to 5,000.

10. A method for creating a PIB-based polymer network, the method comprising:
providing at least two telechelic multi-functional polyisobutylene polymer precursor moieties, each polyisobutylene polymer precursor moiety having at least two end groups selected from the end groups —CH 2 —C(CH 3 )═CH 2 , —CH═C(CH 3 ) 2 , and —CH 2 —CH═CH 2 ;
adding at least one multi-functional thiol with the at least two polyisobutylene polymer precursor moieties to form a mixture, wherein either the at least two telechelic multi-functional polyisobutylene polymer precursor moieties or the at least one multi-functional thiol has three to more functional groups;
irradiating the mixture with light or heat, so as to provide a thiol-ene reaction, thereby producing the PIB-based polymer network; and
wherein the at least one multi-functional thiol is selected from the formulas:
H—S—H,

HS CH 2 n —SH

wherein n is an integer from 1 to 12,

11. The method of claim 10 , wherein each polyisobutylene polymer precursor moiety 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 an end group selected from the groups —CH 2 —C(CH 3 )═CH 2 , —CH═C(CH 3 ) 2 , and —CH 2 —CH═CH 2 .

12. The method of claim 10 , wherein each polyisobutylene polymer precursor moiety has a formula selected from:

wherein m and m′ are each an integer from 2 to 5,000.

13. The method of claim 10 , wherein each polyisobutylene polymer precursor moiety has a formula selected from:

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

14. The method of claim 10 , 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

• C08K5/37

  Thiols · CPC title

• C08F2/10

  Aqueous solvent · CPC title

• C08F299/00

  Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers · CPC title

• C08F110/10 Primary

  Isobutene · CPC title

• C08G75/045

  from mercapto compounds and unsaturated compounds · CPC title