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

Patent metadata

Field	Value
Publication number	US-10730975-B2
Application number	US-201816123601-A
Country	US
Kind code	B2
Filing date	Sep 6, 2018
Priority date	May 20, 2013
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

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 thermoplastic statistical copolymer having a general formula of: [A i -B j -C k ] q ,
wherein:
A represents monomer A, which is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer;
B represents monomer B, which is a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides;
C represents monomer C, which is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer; or a radically polymerizable triglyceride or mixtures thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, provided monomer C is different than the monomer A or monomer B;
i, j, and k are average number of repeating units of monomer A, monomer B, and monomer C, respectively, such that i and j are each greater than 0 and less than 1, k is 0 to less than 1, provided i+j+k=1; and
q represents the number average degree of polymerization and ranges from 10 to 100,000.

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

3. The thermoplastic statistical copolymer of claim 1 , 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.

4. The thermoplastic statistical copolymer of claim 1 , wherein the monomer A and the monomer C, if present, are each independently styrene or methyl (meth)acrylate.

5. The thermoplastic statistical copolymer 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.

6. The thermoplastic statistical copolymer of claim 1 , wherein the triglyceride comprises one or more conjugated sites.

7. The thermoplastic statistical copolymer of claim 1 , wherein the triglyceride is an acrylated epoxidized triglyceride.

8. The thermoplastic statistical copolymer of claim 1 , wherein the monomer C is a radically polymerizable triglyceride or mixtures 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 that of monomer B.

9. The thermoplastic statistical copolymer of claim 1 , wherein the monomer A is styrene, the monomer B is soybean oil, linseed oil, corn oil, flax seed oil, or rapeseed oil, and the monomer C, if present, is a linear chain-extending monomer.

10. In an elastomeric composition, the improvement comprising the thermoplastic statistical copolymer of claim 1 .

11. An elastomer composition comprising the thermoplastic statistical copolymer of claim 1 , wherein the statistical copolymer is vulcanized, cross-linked, compatibilized, and/or compounded with one or more other elastomer, additive, modifier and/or filler.

12. In a toughened engineering thermoplastic composition, the improvement comprising the thermoplastic statistical copolymer of claim 1 .

13. In an asphalt composition, the improvement comprising the thermoplastic statistical copolymer of claim 1 as an asphalt additive, modifier, and/or filler.

14. The asphalt composition of claim 13 further comprising a bitumen component.

15. An adhesive composition comprising:
the thermoplastic statistical copolymer of claim 1 and
a tackifier and/or a plasticizer.

16. In a vehicle tire, the improvement comprising the thermoplastic statistical copolymer of claim 1 .

17. The vehicle tire of claim 16 , wherein the tire is vulcanized, cross-linked, compatibilized, and/or compounded with one or more other material.

Assignees

• Univ Iowa State Res Found Inc

Inventors

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

Classifications

• C08F242/00 Primary

  Copolymers of drying oils with other monomers · CPC title

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08L2555/82

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

• C08F122/20 Primary

  Esters containing oxygen in addition to the carboxy oxygen · CPC title

• C09J153/00

  Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers · CPC title