Functional polymers

Patent metadata

Field	Value
Publication number	US-10174159-B2
Application number	US-201515522487-A
Country	US
Kind code	B2
Filing date	Nov 2, 2015
Priority date	Oct 31, 2014
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

Methods of functionalizing α-halogenated hydroxy acid-based polymers and coupling α-halogenated hydroxy acid-based polymers are provided. Suitable α-halogenated hydroxy acid-based polymers include α-halogenated polyesters and α-halogenated acrylate-based inimers. Methods include coupling α-halogenated polyesters and functionalizing α-halogenated polyesters without polymer cleavage. Certain α-halogenated hydroxy acid-based polymers may be functionalized, crosslinked or, intiate polymerization by inducing the α-halogenated hydroxy acid-based polymers to make a dioxolenium ion intermediate. The α-halogenated hydroxy acid-based polymers may also be functionalized using a radical trap.

First claim

What is claimed is:

1. A method of preparing a functionalized a polymer comprising:
supplying a polyester with α-halogenated groups and a carboxylic acid chain end;
converting the carboxylic acid chain end of the polyester to an acyl chain end to prepare a polyester with α-halogenated groups and an acyl chain end; and
functionalizing at least one of the α-halogenated groups.

2. The method of claim 1 , where the conversion of the carboxylic acid chain end of the polyester to an acyl chain end is performed by first reacting the carboxylic acid chain end with N,N-dimethylchlorosulfitemethaniminium chloride to form an aprotic functional group and then replacing the aprotic functional group with a nucleophile.

3. A method of preparing a coupled polymer comprising:
mixing a plurality of polyesters with α-halogenated groups and a carboxylic acid chain end with N,N-dimethylchlorosulfitemethaniminium chloride.

4. The method of claim 3 , where the plurality of polyesters with α-halogenated groups and a carboxylic acid chain end has an average molecular weight (Mn) prior to the step of mixing with N,N-dimethylchlorosulfitemethaniminium chloride, and the average molecular weight is double after the step of mixing with N,N-dimethylchlorosulfitemethaniminium chloride.

5. A method of crosslinking an α-halogenated polymer comprising:
inducing the formulation of a dioxolenium ion intermediate in an α-halogenated polymer that includes a unit defined by the formula

where X is a halogen atom, and
reacting the dioxolenium ion intermediate with an activated aromatic ring or an activated polyaromatic compound.

6. The method of claim 5 , where the α-halogenated polymer is an α-halogenated polyester.

7. The method of claim 5 , where the α-halogenated polymer is a hyperbranched α-halogenated polymer.

8. The method of claim 5 , where the step of inducing the formulation of a dioxolenium ion intermediate is performed by in the presence of a silver salt.

9. The method of claim 5 , where the step of inducing the formulation of a dioxolenium ion intermediate is performed by heating the α-halogenated polymer.

10. The method of claim 5 , where the dioxolenium ion intermediate is reacted with an activated polyaromatic compound and the activated polyaromatic compound is defined by the formula;
Ar—R 13 —Ar

where each Ar is individually an aromatic group and R 13 is an electron-donating organic group.

11. A method of functionalizing an α-halogenated polymer comprising:
inducing the formulation of a dioxolenium ion intermediate in an α-halogenated polymer that includes a unit defined by the formula

where X is a halogen, and
reacting the dioxolenium ion intermediate with an activated aromatic ring.

12. The method of claim 11 , where the α-halogenated polymer is an α-halogenated polyester.

13. The method of claim 11 , where the α-halogenated polymer is a hyperbranched α-halogenated polymer.

14. The method of claim 11 , where the step of inducing the formulation of a dioxolenium ion intermediate is performed by in the presence of a silver salt.

15. The method of claim 11 , where the step of inducing the formulation of a dioxolenium ion intermediate is performed by heating the α-halogenated polymer.

16. The method of claim 11 , where the activated aromatic ring is defined by the formula;
Ar—R 14

where Ar is an aromatic group and R 14 is an electron-donating organic group.

17. A method of preparing an α-halogenated polymer with a polymeric or oligomeric side-chain comprising:
supplying monomer;
initiating the monomer by producing a dioxolenium ion intermediate in an α-halogenated polymer that includes a unit defined by the formula

where X is a halogen atom.

18. The method of claim 17 , where the α-halogenated polymer is an α-halogenated polyester.

19. The method of claim 17 , where the α-halogenated polymer is a hyperbranched α-halogenated polymer.

20. The method of claim 17 , where the step of inducing the formulation of a dioxolenium ion intermediate is performed by in the presence of a silver salt, and the polymerization of the monomer is initiated through cationic initiation.

21. The method of claim 17 , where the step of inducing the formulation of a dioxolenium ion intermediate is performed by heating the α-halogenated polymer, and the polymerization of the monomer is initiated through cationic initiation.

22. A method of preparing a functionalized a polymer comprising:
reacting TEMPO compound and an α-halogenated polymer that includes a unit defined by the formula

where X is a halogen atom.

23. The method of claim 22 , where the TEMPO compound is defined by the formula:

where R 15 is a monovalent organic group.

Assignees

• Pugh Coleen
• Wright Colin
• Scherger Carolyn
• Yan Xiang
• Zhang Zheng
• Wang Zewei
• Univ Akron

Inventors

• Pugh Coleen
• Wright Colin
• Scherger Carolyn
• Yan Xiang
• Zhang Zheng
• Wang Zewei

Classifications

• C08G63/91

  Polymers modified by chemical after-treatment · CPC title

• C08G63/6822 Primary

  derived from hydroxy carboxylic acids · CPC title

• C08G63/912

  derived from hydroxycarboxylic acids · CPC title

• C08G63/682

  containing halogens · CPC title