Star isobutylene-based thermoplastic elastomers

Patent metadata

Field	Value
Publication number	US-10626211-B2
Application number	US-201916532800-A
Country	US
Kind code	B2
Filing date	Aug 6, 2019
Priority date	Aug 6, 2018
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

A star block copolymer and a thermoplastic elastomer including plurality of the star block copolymers and a method of making both is taught. The star block copolymers of the present invention include a core component having an α-methylstyrene oligomer wherein arms emanate from the core component and the arms are poly(isobutylene-block-styrene) diblock copolymers.

First claim

What is claimed is:

1. A star block copolymer comprising a core component including an α-methylstyrene oligomer and arms emanating from the core component, wherein the arms are poly(isobutylene-block-styrene) diblock copolymers.

2. The star block copolymer of claim 1 wherein the α-methylstyrene oligomer contains between 3 and 10 α-methylstyrene units and wherein each α-methylstyrene unit has a single poly(isobutylene-block-styrene) diblock copolymer arm emanating from a styrene portion of the oligomer.

3. The star block copolymer of claim 2 wherein the number average molecular weight of each polyisobutylene block of each poly(isobutylene-block-styrene) diblock copolymer arm is between about 30,000 and about 40,000 g/mol and wherein the number average molecular weight of each polystyrene block of each poly(isobutylene-block-styrene) diblock copolymer arm is between about 12,000 and about 14,000 g/mol.

4. The star block copolymer of claim 1 having a tensile strength of greater than 20 MPa.

5. The star block copolymer of claim 1 having essentially no creep deformation.

6. A method of producing a star block copolymer comprising a core component having an α-methylstyrene oligomer and arms emanating from the core component wherein the arms are poly(isobutylene-block-styrene) diblock copolymers, the method including the steps of:
a. synthesizing α-methylstyrene oligomer;
b. acetylating the α-methylstyrene oligomer to form an α-methylstyrene oligomer with acetyl groups;
c. converting the acetyl groups to cumyl hydroxide groups;
d. undertaking living carbocationic polymerization of isobutylene to form polyisobutylene blocks; and
e. undertaking living carbocationic polymerization of styrene to form polystyrene blocks at an end of each polyisobutylene block to provide the poly(isobutylene-block-styrene) diblock copolymer arms.

7. The method of claim 6 wherein the step of synthesizing includes adding n-BuLi to α-methylstyrene under strong stirring for a period of about 5 hours, followed by the termination of the synthesis by the addition of methanol.

8. The method of claim 7 wherein the step of acetylating includes combining the α-methylstyrene oligomer with AlCl 3 , CH 2 Cl 2 , and CH 3 COCl so as to form the α-methylstyrene oligomer with acetyl groups.

9. The method of claim 8 wherein the step of converting the acetyl groups to cumyl hydroxide groups takes place utilizing the Grignard reaction to form a α-methylstyrene oligomer with cumyl hydroxide groups.

10. The method of claim 9 wherein the step of undertaking living carbocationic polymerization of isobutylene includes adding the α-methylstyrene oligomer with cumyl hydroxide groups to isobutylene and a TiCl 4 coinitiator to form a living intermediate.

11. The method of claim 10 wherein the step of undertaking living carbocationic polymerization includes adding styrene to the living intermediate, followed by the termination of the living carbocationic polymerization by the addition of methanol.

12. A thermoplastic elastomer including a plurality of star block copolymers comprising a core component including an α-methylstyrene oligomer and arms emanating from the core component, wherein the arms are poly(isobutylene-block-styrene) diblock copolymers and wherein at least some of the polystyrene blocks of the plurality of star block copolymers are physically crosslinked through aggregation.

13. The star-thermoplastic elastomer of claim 12 wherein the α-methylstyrene oligomer of each of the plurality of star block copolymers contains between 3 and 10 α-methylstyrene units and wherein each α-methylstyrene unit has a single poly(isobutylene-block-styrene) diblock copolymer arm emanating from a styrene portion of the oligomer.

14. The star-thermoplastic elastomer of claim 13 wherein the number average molecular weight of each polyisobutylene block of each poly(isobutylene-block-styrene) diblock copolymer arm is between about 30,000 and about 40,000 g/mol and wherein the number average molecular weight of each polystyrene block of each poly(isobutylene-block-styrene) diblock copolymer arm is between about 12,000 and about 14,000 g/mol.

Assignees

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

Inventors

• Kennedy Joseph
• Nugay Turgut
• Nugay Nihan

Classifications

• C08F8/02

  Alkylation · CPC title

• C08F210/10

  Isobutene · CPC title

• C08F8/10

  Acylation · CPC title

• C08F297/00 Primary

  Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer · CPC title

• C08L25/16

  Homopolymers or copolymers of alkyl-substituted styrenes · CPC title