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

Patent metadata

Field	Value
Publication number	US-10093758-B2
Application number	US-201815895888-A
Country	US
Kind code	B2
Filing date	Feb 13, 2018
Priority date	May 20, 2013
Publication date	Oct 9, 2018
Grant date	Oct 9, 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 statistical copolymer, said method comprising:
providing a radically polymerizable monomer, represented by A;
providing a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, represented by B; and
polymerizing monomer A and monomer B simultaneously, 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 statistical copolymer, wherein said polymerizing is carried out under conditions effective to achieve a number average degree of polymerization (N n ) for the thermoplastic statistical copolymer of up to 100,000 without gelation.

2. The method of claim 1 further comprising, prior to said polymerizing:
providing a radically polymerizable monomer, represented by C, wherein monomer C is different than monomer A or monomer B, wherein said polymerizing comprises polymerizing monomer A, monomer B, and monomer C simultaneously, via RAFT, in the presence of the free radical initiator and the chain transfer agent to form the thermoplastic statistical copolymer.

3. The method of claim 1 , wherein said polymerizing is carried out at a molar ratio of the chain transfer agent to the monomer ranging from 1:1 to 50:1.

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

5. The method of claim 1 , wherein the monomer A and the monomer C, if present, are each independently vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer.

6. The method of claim 5 , wherein the monomer A and the monomer C, if present, are each independently selected from the group consisting of styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, vinyl acetate, N-vinylpyrrolidone, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, and mixtures thereof.

7. The method of claim 6 , wherein the monomer A and the monomer C, if present, are each independently styrene or methyl (meth)acrylate.

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

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

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

11. The method of claim 2 , wherein the monomer C is a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, wherein the monomer C is from a different plant oil or animal oil than the monomer B, or the triglycerides of the monomer C have a different degree of conjugation than the monomer B.

12. The method of claim 1 , wherein the monomer A is styrene, the monomer B is soybean oil, and the monomer C, if present, is a linear chain-extending monomer.

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

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

15. 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-pentanol, 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,-tetrachloroethane, 1,1,1,-trichloroethane, tetrachloroethylene, tetrachloromethane, trichloroethylene, water, xylene, benzene, nitromethane, or a mixture thereof.

16. The method of claim 14 , wherein said polymerizing is carried out in a solvent with the monomers being dissolved in the solvent at a concentration ranging from 5% to 100 wt %.

17. The method of claim 14 , wherein said polymerizing is carried out in a solvent with the monomers being dissolved in the solvent at a concentration ranging from 10% to 40 wt %.

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

19. 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.

20. The method of claim 1 , wherein the chain transfer agent is 1-phenylethyl benzodithioate or 1-phenylethyl 2-phenylpropanedithioate.

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

• 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

• C08L2555/82

  from natural renewable resources, e.g. starch, cellulose, saw dust, straw, hair or shells · CPC title