Synthesis of hyperbranched polyacrylates by emulsion polymerizsation of inimers

Patent metadata

Field	Value
Publication number	US-9777082-B2
Application number	US-201213646215-A
Country	US
Kind code	B2
Filing date	Oct 5, 2012
Priority date	Oct 5, 2011
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

A method for the production of hyperbranched polyacrylates includes the step of reacting acrylic inimers through controlled living polymerization in aqueous conditions. The inimers may have the formula:

Wherein X is a halogen, a thiocarbonylthio or nitroxide group, and R is hydrogen, methyl, dodecyl, and groups containing mesogenin substituents, fluorocarbon substituents, siloxane substituents and oxyethylene substituents. In particular, the aqueous condition is emulsion or miniemulsion. The polymerization may be reverse ATRP, SN&RI and AGET polymerization or RAFT polymerization (with thiocarbonylthio X groups) or nitroxide mediated polyeization (with nitroxide X groups).

First claim

What is claimed is:

1. A method for the production of hyperbranched polyacrylates comprising the step of:
reacting acrylic inimers through controlled living polymerization in aqueous conditions to produce a hyperbranched polyacrylate with a number average molecular weight determined by gel permeation chromatography relative to calibration curves prepared using linear polystyrene from 50,000 Da to 1,000,000 Da; wherein the hyperbranched polyacrylate has a polydispersity index from 1.0 to 5; wherein the controlled living polymerization is carried out in emulsion or in miniemulsion.

2. The method of claim 1 , wherein the controlled living polymerization is selected from atom transfer radical polymerization (ATRP), reverse ATPRP, simultaneous normal and radical initiated (SN&RI) polymerization, activators generated by electron transfer (AGET) ATRP, reversible addition-fragmentation chain-transfer (RAFT) polymerization, and nitroxide mediated polymerization.

3. The method of claim 2 , wherein the polymerization is carried out in a miniemulsion.

4. The method of claim 1 , wherein the acrylic inimer is:

wherein X is a halogen and R is selected from hydrogen, methyl, dodecyl, and groups containing mesogenin substituents, fluorocarbon substituents, siloxane substituents and oxyethylene substituents.

5. The method of claim 4 , wherein the controlled living polymerization is selected from reverse ATRP, SN&RI and AGET polymerization.

6. The method of claim 1 , wherein the acrylic inimer is:

wherein X is a thiocarbonylthio group and R is selected from hydrogen, methyl, dodecyl, and groups containing mesogenin substituents, fluorocarbon substituents, siloxane substituents and oxyethylene substituents.

7. The method of claim 6 , wherein the controlled living polymerization is RAFT polymerization.

8. The method of claim 1 , wherein the acrylic inimer is:

wherein X is a nitroxide group and R is selected from hydrogen, methyl, dodecyl, and groups containing mesogenin substituents, fluorocarbon substituents, siloxane substituents and oxyethylene substituents.

9. The method of claim 8 , wherein the controlled living polymerization is nitroxide mediated polymerization.

10. The method of claim 1 , where the hyperbranched polyacrylate has a number average molecular weight from 50,000 Da to 500,000 Da.

Assignees

• Univ Akron

Inventors

• Pugh Coleen
• Garcia Guillermina

Classifications

• C08F26/06 Primary

  by a heterocyclic ring containing nitrogen · CPC title

• C08G83/005

  Hyperbranched macromolecules · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title

• C08F2438/01

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

• C08F220/40

  Esters of unsaturated alcohols {, e.g. allyl (meth)acrylate} · CPC title