Densely functionalized polymers derived from baylis-hillman adducts

Patent metadata

Field	Value
Publication number	US-9963540-B2
Application number	US-201414776006-A
Country	US
Kind code	B2
Filing date	Mar 14, 2014
Priority date	Mar 14, 2013
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

A method of preparing a polymer is provided comprising preparing a Baylis-Hillman adduct by reacting an activated alkene with a carbon electrophile; and polymerizing the Baylis-Hillman adduct. The Baylis-Hillman reaction provides an efficient platform for the synthesis of densely functionalized monomers, from which polymers with multiple functional groups can be readily synthesized. It has been discovered that that Baylis-Hillman adducts are versatile monomers for both controlled radical and step-growth polymerizations.

First claim

What is claimed is:

1. A method of preparing a polymer comprising:
preparing a diol functionalized Baylis-Hillman adduct by performing a Baylis-Hillman reaction on an activated alkene and a carbon electrophile, and polymerizing the diol functionalized Baylis-Hillman adduct through a step-growth polymerization to produce a polymer defined by the formula:

where R 4 and R 8 are each independently hydrocarbon groups; R 5 is a bond or a hydrocarbon group; Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group; each X is an ester or urethane group; and n is about 10 to 100 units; or a polymer defined by the formula:

where R 4 and R 8 are each independently hydrocarbon groups; R 5 is a bond or a hydrocarbon group; Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group; and Z 2 is a hydrogen atom, aryl group, protected amine, protected carboxylic acid, alkoxy, silyloxy, hydroxyl, protected diol, amine, carboxylic acid, or diol; each X is an ester or urethane group; and n is about 10 to 100.

2. The method of claim 1 , where the activated alkene is defined by the formula:

and the carbon electrophile is defined by the formula

where R 4 is a hydrocarbon group; R 5 is a bond or a hydrocarbon group; and Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group.

3. The method of claim 1 , where the step-growth polymerization prepares a polyurethane by reacting a diisocyanate and the Baylis-Hillman adduct.

4. The method of claim 3 , where the diisocyante may be defined by the formula:
O═C═N—R 8 —N═C═O

where R 8 is a hydrocarbon group.

5. The method of claim 3 , where the diol functionalized Baylis-Hillman adduct is modified prior to polymerization through a reaction with a thiol compound to provide a diol functionalized Baylis-Hillman adduct defined by the formula:

where R 4 is a hydrocarbon groups; each R 5 is independently a bond or a hydrocarbon group; Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group; and Z 2 is a hydrogen atom, protected amine, protected carboxylic acid, alkoxy, or silyloxy, hydroxyl group, protected diol or aryl group.

6. The method of claim 3 , where the diol functionalized Baylis-Hillman adduct is defined by the formula:

where R 4 is a hydrocarbon group; R 5 is a bond or a hydrocarbon group; and Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group.

7. The method of claim 6 , where the polymer is modified post-polymerization by a thiol-ene reaction.

8. The method of claim 7 , where the thiol-ene reaction is preformed with a thiol compound defined by the formula:
Z 2 —R 5 —SH

where R 5 is independently a bond or a hydrocarbon group, and Z 2 is a hydrogen atom, aryl group, protected amine, protected carboxylic acid, alkoxy, silyloxy, hydroxyl, protected diol, amine, carboxylic acid, or diol.

9. The method of claim 1 , where diol functional Baylis-Hillman adduct is first modified prior to polymerization through the addition of a functional group through a thiol-ene reaction, and the step-growth polymerization prepares polyester by reacting a dicarboxylic acid and the Baylis-Hillman adduct.

10. The method of claim 9 , the dicarboxylic acid is defined by the formula:

where R 8 is a hydrocarbon group.

11. The method of claim 9 , where thiol-modified diol functionalized Baylis-Hillman is defined by the formula:

where R 4 is a hydrocarbon groups; each R 5 is independently a bond or a hydrocarbon group; Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group; and Z 2 is a hydrogen atom, protected amine, protected carboxylic acid, alkoxy, or silyloxy, hydroxyl group, protected diol or aryl group.

12. A polymer defined by the formula:

where R 4 and R 8 are each independently hydrocarbon groups; R 5 is a bond or a hydrocarbon group; Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group; each X is an ester or urethane group; and n is about 10 to 100 units.

13. The polymer of claim 12 , where each X is an ester group.

14. The polymer of claim 12 , where each X is a urethane group.

15. A polymer defined by the formula:

where R 4 and R 8 are each independently hydrocarbon groups; R 5 is a bond or a hydrocarbon group; Z 1 is hydrogen, protected amine, protected carboxylic acid, protected hydroxyl, alkoxy, or silyloxy group; and Z 2 is a hydrogen atom, aryl group, protected amine, protected carboxylic acid, alkoxy, silyloxy, hydroxyl, protected diol, amine, carboxylic acid, or diol; each X is an ester or urethane group; and n is about 10 to 100.

16. The polymer of claim 15 , where each X is a urethane group.

Assignees

• Joy Abraham
• Peng Chao
• Univ Akron

Inventors

• Joy Abraham
• Peng Chao

Classifications

• C08G18/73

  acyclic · CPC title

• C08G18/34

  Carboxylic acids; Esters thereof with monohydroxyl compounds · CPC title

• C08G18/3868

  the sulfur atom belonging to a sulfide group · CPC title

• C08K2201/011

  Nanostructured additives · CPC title

• C08G18/67 Primary

  Unsaturated compounds having active hydrogen · CPC title