Thermoplastic elastomers via reversible addition-fragmentation chain transfer polymerization of triglycerides

Patent metadata

Field	Value
Publication number	US-9926392-B2
Application number	US-201715487570-A
Country	US
Kind code	B2
Filing date	Apr 14, 2017
Priority date	May 20, 2013
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

The present invention relates to a thermoplastic block copolymer comprising at least one PA block and at least one PB block. The PA block represents a polymer block comprising one or more units of monomer A, and the PB block represents a polymer block comprising one or more units of monomer B. Monomer A is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer. Monomer B is a radically polymerizable triglyceride or mixtures thereof, typically in the form of a plant or animal oil. The present invention also relates to a method of preparing a thermoplastic block copolymer or novel thermoplastic statistical copolymers by polymerizing a radically polymerizable monomer with a radically polymerizable triglyceride or mixtures thereof via reversible addition-fragmentation chain-transfer polymerization (RAFT), in the presence of an free radical initiator and a chain transfer agent.

First claim

What is claimed:

1. A method of preparing a thermoplastic homopolymer, said method comprising: providing a radically polymerizable triglyceride, in the form of a plant oil, animal oil, or synthetic triglyceride monomer; and polymerizing said plant oil monomer, animal oil or synthetic triglyceride monomer via reversible addition-fragmentation chain-transfer polymerization (RAFT), in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic homopolymer, wherein said polymerizing is carried out under conditions effective to achieve a number average degree of polymerization (N n ) for the thermoplastic homopolymer of up to 100,000 without gelation.

2. The method of claim 1 , wherein the chain transfer agent to the monomer molar ratio ranges from 1:1 to 50:1.

3. The method of claim 1 further comprising:
catalytically hydrogenating reactive unsaturated sites in the thermoplastic homopolymer to partial or full saturation after said polymerizing.

4. The method of claim 1 , wherein the monomer is a radically polymerizable plant oil monomer selected from the group consisting of soybean oil, linseed oil, corn oil, flax seed oil, and rapeseed oil.

5. The method of claim 1 , wherein the triglyceride comprises one or more conjugated sites.

6. The method of claim 1 , wherein the triglyceride is an acrylated epoxidized triglyceride.

7. The method of claim 1 , wherein said polymerizing is carried out at a temperature of 0 to 150° C.

8. The method of claim 1 , wherein said polymerizing is carried out in a solvent at a temperature of 50 to 85° C.

9. The method of claim 1 , wherein said polymerizing is carried out in a solvent with the solvent being toluene, THF, chloroform, cyclohexane, dioxane, dimethyl sulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentnaol, chlorobenzene, dichloromethane, diethylether, tert-butanol, 1,2-dichloroethylene, diisopropylether, ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropylalcohol, isoamylalcohol, methanol, pentane, n-propylacohol, pentachloroethane, 1,1,2,2-tetrachloro ethane, 1,1,1-trichloroethane, tetrachloroethylene, tetrachloromethane, trichloroethylene, water, xylene, benzene, nitromethane, or a mixture thereof.

10. The method of claim 1 , wherein said polymerizing is carried out in a solvent with the monomer having a concentration, when dissolved in the solvent, ranging from 5% to 100 wt %.

11. The method of claim 1 , wherein said polymerizing is carried out in a solvent with the monomer having a concentration, when dissolved in the solvent, ranging from 10% to 40 wt %.

12. The method of claim 1 , wherein the initiator is benzoyl peroxide or azobisisobutyronitrile.

13. The method of claim 1 , wherein the chain transfer agent is a thiocarbonylthio compound, a dithioester compound, a trithiocarbonate compound, a dithiocarbamate compound, or a xantate compound capable of reversible association with polymerizable free radicals.

14. The method of claim 13 , wherein the chain transfer agent is 1-phenylethyl benzodithioate, 1-phenylethyl 2-phenylpropanedithioate, or dibenzyl carbonotrithioate.

Assignees

• Univ Iowa State Res Found Inc

Inventors

• Cochran Eric W
• Williams Ronald Christopher
• Hernandez Nacu
• Cascione Andrew

Classifications

• C08F222/1006

  of polyhydric alcohols or polyhydric phenols · CPC title

• C08F222/103

  of trialcohols, e.g. trimethylolpropane tri(meth)acrylate · CPC title

• C08L2555/80

  Macromolecular constituents · CPC title

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title