Centrally functionalizable living cationic polymer or copolymer and methods of synthesizing the same

Patent metadata

Field	Value
Publication number	US-10774185-B2
Application number	US-201916257582-A
Country	US
Kind code	B2
Filing date	Jan 25, 2019
Priority date	Jan 25, 2018
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

In various embodiments, the present invention is directed to a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group having the formula

wherein each R is selected from the group consisting of a polymer or a copolymer, such as a polyisobutylene polymer or a poly(isobutylene-b-styrene) copolymer.

First claim

What is claimed is:

1. A centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group having the formula

wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

2. The centrally-functionalizable living cationic polymer or copolymer of claim 1 , wherein each R is a polyisobutylene polymer.

3. The centrally-functionalizable living cationic polymer or copolymer of claim 1 , wherein each R is a poly(isobutylene-b-styrene) copolymer.

4. A method of synthesizing a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group comprising:
a. initiating living cationic polymerization so as to form a non-centrally functionalizable living cationic polymer or copolymer having the formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer; and

b. thermolyzing the formed non-centrally functionalizable living cationic polymer or copolymer such that a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group is formed having the formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

5. The method of claim 4 , wherein each R is a polyisobutylene polymer.

6. The method of claim 4 , wherein each R is a poly(isobutylene-b-styrene) copolymer.

7. The method of claim 4 , wherein the step of initiating utilizes a bi-directional initiator defined by the formula:

wherein X is the same and selected from the group consisting of Cl, OH, and OCH 3 .

8. The method of claim 4 , wherein the step of thermolyzing takes place in the presence of a solvent and wherein the solvent is selected from the group consisting of mesitylene, durene, liquid paraffine, paraffine wax, and mineral oil.

9. The method of claim 4 , wherein the step of thermolyzing takes place in the absence of a solvent.

10. The method of claim 4 , further comprising the step of epoxodizing the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group.

11. The method of claim 10 , wherein the step of epoxodizing forms a polymer or copolymer having the formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

12. The method of claim 11 , further comprising the step of taking the polymer or copolymer formed by the step of epoxodizing and polymerizing said polymer or copolymer with ethylene oxide.

13. The method of claim 12 , wherein the step of polymerizing with ethylene oxide forms a polymer or copolymer having the formula:

wherein n is a number from 10 to 1,000 and wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

14. The method of claim 11 , further comprising the step of taking the polymer or copolymer formed by the step of epoxodizing and reacting the polymer or copolymer with 2-bromo-2-methyl propionic acid to form an atom transfer radical polymerization macroinitiator having the formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer,
followed by atom transfer radical polymerization with t-butyl acrylate to form a polymer or copolymer having the formula:

wherein n is a number from 10 to 10,000 and wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

15. The method of claim 14 , further comprising reacting with trifluoroacetic acid to form a polymer or copolymer having the formula:

wherein n is a number from 10 to 10,000 and wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

16. The method of claim 5 , further comprising the step of performing hydrosulfuration on the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group.

17. The method of claim 16 , wherein the step of performing hydrosulfuration forms a polymer or copolymer having the formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

18. The method of claim 5 , further comprising the step of performing hydrosilation on the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group.

19. The method of claim 18 , wherein the step of performing hydrosilation forms a polymer or copolymer having the formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

20. The method of claim 4 , further comprising the step of reacting the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group with a dienophile.

21. The method of claim 20 , wherein the step of reacting the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group with a dienophile forms a polymer or copolymer having the following formula:

wherein each R is the same and selected from the group consisting of a polymer or a copolymer.

22. A method of synthesizing a polyurethane utilizing a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group as the starting material, the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group having the formula:

wherein each R is selected from the group consisting of a polymer or a copolymer.

Assignees

• Kennedy Joseph P
• Nugay Turgut
• Nugay Nihan
• Deodhar Tejal J
• Dollinger Susan
• Univ Akron

Inventors

• Kennedy Joseph P
• Nugay Turgut
• Nugay Nihan
• Deodhar Tejal J
• Dollinger Susan

Classifications

• C08G81/025 Primary

  containing polyether sequences · CPC title

• C08G65/14 Primary

  Unsaturated oxiranes · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title

• C08F2438/00

  Living radical polymerisation · CPC title