Polyisobutylene-based thermoplastic elastomers

Patent metadata

Field	Value
Publication number	US-10280130-B2
Application number	US-201715590431-A
Country	US
Kind code	B2
Filing date	May 9, 2017
Priority date	Aug 10, 2012
Publication date	May 7, 2019
Grant date	May 7, 2019

Abstract

The present invention is directed to a new class of thermoplastic elastomers (TPEs) and processes for making them. In some embodiments of the present invention, the end groups of the multi-arm PIB copolymer is a conjugated diene, whereas the other component is a multi-functional dienophile. The components of the TPE of the present invention are chemically connected via the well-known Diels-Alder reaction which is thermally reversible (by the retro-Diels-Alder reaction) at moderately elevated temperatures. The reversibility of the Diels-Alder retro-Diels-Alder reactions allows the recovery of the original components of the TPE and thus its recyclability and also gives the TPE the ability to be reshaped or reformed.

First claim

What is claimed is:

1. A multi-arm polyisobutylene (PIB) polymer comprising:
a) an oligomeric styrene pre-polymer having a sec-butyl head group, a poly(α-methylstyrene) segment from 3 to 5 units in length and a poly[3-(2-methoxyisopropyl)styrene] segment from 3 units to 50 units in length and having the structure of formula (v):

 wherein n is an integer from 3 to 5 and m is an integer from 3 to 50; and
b) at least one PIB arm extending from each 3-(2-methoxyisopropyl)styrene wherein said PIB arms are terminated with end groups selected from the group consisting of allyls, dienes, and furans.

2. The multi-arm PIB polymer of claim 1 wherein said end groups are allyl end groups.

3. The multi-arm PIB polymer claim 2 having the formula (vi):

wherein n is an integer from 3 to about 5, m is an integer from 3 to 50, and q is an integer from 10 to 10,000.

4. The multi-arm PIB polymer of claim 1 wherein said end groups are diene end groups.

5. The multi-arm PIB polymer of claim 1 wherein said end groups are furan end groups.

6. The multi-arm PIB polymer of claim 5 having the formula (vii):

wherein n is an integer from 2 to 5, m is an integer from 3 to 50, and q is an integer from 10 to 10,000.

7. A method for making a thermoplastic elastomer network comprising reacting: the multi-arm polyisobutylene polymer of claim 1 ; a plurality of multi-functional dienophiles; and a plurality of tris-furan molecules to form a reversibly crosslinked thermoplastic elastomer.

8. A method for synthesizing a multi-arm polyisobutylene having an oligomeric styrene, a sec-butyl head group, and allyl end groups comprising:
a) reacting a sec-butyl lithium and an α-methylstyrene to form an α-methylstyrene oligomer of from 3 units to 5 units in length, said α-methylstyrene oligomer having a sec-butyl head group and a lithium ion;
b) reacting the α-methylstyrene oligomer of step (a) with potassium tert-butoxide to replace the lithium ion on the α-methylstyrene oligomer with a potassium ion;
c) reacting the methylstyrene oligomer of step (b) with a 3-(2-methoxyisopropyl)styrene to form an oligomeric styrene pre-polymer having a sec-butyl head group, a poly(α-methylstyrene) segment of from 3 to 5 units in length, and a poly[3-(2-methoxyisopropyl)styrene] segment of from 3 to 50 units in length;
d) combining the oligomeric styrene pre-polymer of step (c), a stoichiometric excess of isobutylene, and a photoinitiator, wherein said isobutylene is added to at least one of the 3-(2-methoxyisopropyl)styrene units of said poly[3-(2-methoxyisopropyl)styrene] segment of said oligomeric styrene pre-polymer by cationic polymerization to create PIB arms of from 10 units to 10,000 units in length extending from each of said 3-(2-methoxyisopropyl)styrene units; and
e) adding allyltrimethylsilane to terminate the isobutylene polymerization and place an allyl end group on the end of said PIB arms.

9. A method for synthesizing a multi-arm polyisobutylene having an oligomeric styrene, a sec-butyl head group, and diene end groups comprising:
a) dissolving the allyl-terminated multi-arm polyisobutylene of claim 3 and a photoinitiator in a solvent to provide a solution;
b) adding furfuryl mercaptan to provide a solution comprising furfuryl mercaptan and the solution of step (a);
c) irradiating the solution of step (b); and
d) removing the solvent to provide a multi-arm polyisobutylene having an oligomeric styrene, a sec-butyl head group, and diene end groups.

10. The method of claim 9 further comprising the steps of:
e) redissolving the multi-arm polyisobutylene having an oligomeric styrene, a sec-butyl head group, and a diene end groups of step (d) in hexane;
f) washing the solution of step (e) with methanol; and
g) removing said hexane and said methanol under reduced pressure to leave the multi-arm polyisobutylene having an oligomeric styrene, a sec-butyl head group, and a diene end groups.

11. The method of claim 9 wherein the photoinitiator is 2,2-dimethoxy-2-phenyl acetophenone and the solvent is dichloromethane.

12. A method for making a thermoplastic elastomer network comprising reacting the multi-arm polyisobutylene having an oligomeric styrene, a sec-butyl head group, and a diene end groups of claim 9 and a plurality of multi-functional dienophiles to form a reversibly crosslinked thermoplastic elastomer.

13. The method of claim 12 , wherein said diene end groups are a furan end groups.

14. The method of claim 12 , wherein said multi-functional dienophiles are selected from the group consisting of aliphatic/aromatic bis-maleimide, tris-maleimide, and combinations thereof.

Assignees

• Univ Akron

Inventors

• Kennedy Joseph P
• Nugay Turgut
• Nugay Nihan

Classifications

• C08J3/28

  Treatment by wave energy or particle radiation · CPC title

• C07C41/09

  by dehydration of compounds containing hydroxy groups · CPC title

• C08J2351/06

  grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond · CPC title

• C07C43/166

  having unsaturation outside the aromatic rings · CPC title

• C07C29/72 Primary

  by oxidation of carbon-to-metal bonds · CPC title