Initiation of controlled radical polymerization from lactide monomer

Patent metadata

Field	Value
Publication number	US-9879103-B2
Application number	US-201514833080-A
Country	US
Kind code	B2
Filing date	Aug 22, 2015
Priority date	Apr 2, 2014
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

A lactide-functionalized polymer is synthesized by polymerizing a monomer capable of undergoing radical polymerization (e.g., styrenic, vinylic, acrylic, etc.) using a brominated lactide initiator via atom transfer radical polymerization (ATRP). In some embodiments of the present invention, the brominated lactide initiator is 3-bromo-3,6-dimethyl-1,4-dioxane-2,5-dione prepared by reacting lactide with N-bromosuccinimide in the presence of benzoyl peroxide.

First claim

What is claimed is:

1. A method for synthesizing a lactide-functionalized polymer, comprising:
polymerizing a monomer using a brominated lactide initiator via atom transfer radical polymerization (ATRP), wherein the brominated lactide initiator is 3-bromo-3,6-dimethyl-1,4-dioxane-2,5-dione and wherein the monomer is represented by the following formula:

wherein R is a hydrogen atom or a methyl group, and wherein R′ is a phenyl group or C(O)OR″, wherein R″ is an alkyl group having one or more carbon atoms.

2. The method as recited in claim 1 , wherein the monomer is selected from the group consisting of styrene, butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, 2-ethylhexl methacrylate, ethyl methacrylate, butyl methacrylate, and combinations thereof.

3. The method as recited in claim 1 , wherein the monomer is styrene.

4. The method as recited in claim 1 , wherein the monomer is butyl acrylate.

5. The method as recited in claim 1 , wherein the step of polymerizing a monomer using the brominated lactide initiator via atom transfer radical polymerization (ATRP) comprises the step of preparing a catalytic copper/ligand complex comprising a copper(I) complex and a ligand with a slight excess of copper prior to adding the brominated lactide initiator to the copper/ligand complex.

6. The method as recited in claim 1 , further comprising the step of:
reacting lactide with N-bromosuccinimide in the presence of benzoyl peroxide to prepare the bromated lactide initiator.

7. The method as recited in claim 1 , further comprising the step of:
reacting lactide with bromine (Br 2 ) in the presence of benzoyl peroxide to prepare the bromated lactide initiator.

8. A method for synthesizing a lactide-functionalized polymer, comprising:
preparing a brominated lactide initiator, wherein the brominated lactide initiator is 3-bromo-3,6-dimethyl-1,4-dioxane-2,5-dione;
polymerizing a monomer using the brominated lactide initiator via atom transfer radical polymerization (ATRP), wherein the monomer is represented by the following formula:

wherein R is a hydrogen atom or a methyl group, and wherein R′ is a phenyl group or C(O)OR″, wherein R″ is an alkyl group having one or more carbon atoms.

9. The method as recited in claim 8 , wherein the monomer is selected from the group consisting of styrene, butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, 2-ethylhexl methacrylate, ethyl methacrylate, butyl methacrylate, and combinations thereof.

10. The method as recited in claim 8 , wherein the monomer is styrene.

11. The method as recited in claim 8 , wherein the monomer is butyl acrylate.

12. The method as recited in claim 8 , wherein the step of polymerizing a monomer using the brominated lactide initiator via atom transfer radical polymerization (ATRP) comprises the step of preparing a catalytic copper/ligand complex comprising a copper(I) complex and a ligand with a slight excess of copper prior to adding the brominated lactide initiator to the copper/ligand complex.

13. The method as recited in claim 8 , wherein the step of preparing a brominated lactide initiator comprises the step of reacting lactide with N-bromosuccinimide in the presence of benzoyl peroxide.

14. The method as recited in claim 8 , wherein the step of preparing a brominated lactide initiator comprises the step of reacting lactide with bromine (Br 2 ) in the presence of benzoyl peroxide.

Assignees

• IBM

Inventors

• Boday Dylan J
• Mauldin Timothy C

Classifications

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08F120/18 Primary

  with acrylic or methacrylic acids · CPC title

• C08F112/08

  Styrene · CPC title

• C08F120/10 Primary

  Esters · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title