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

Patent metadata

Field	Value
Publication number	US-9650463-B2
Application number	US-201414282737-A
Country	US
Kind code	B2
Filing date	May 20, 2014
Priority date	May 20, 2013
Publication date	May 16, 2017
Grant date	May 16, 2017

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 block copolymer comprising at least one PA block and at least one PB block, wherein PA represents a polymer block comprising one or more units of monomer A and PB represents a branched-chain polymer block comprising one or more units of monomer B, with monomer A being a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer, and monomer B being a, radically polymerizable triglyceride or mixtures thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, wherein one end or both ends of the PA block or PB block is functionalized with a thiocarbonylthio chain transfer group, wherein said block copolymer has a number average degree of polymerization (N) of up to 100,000 without gelation.

2. A telechelic thermoplastic block copolymer having an architecture of (PA-PB) n -TCTA-(PB-PA) n or (PB-PA) n -TCTA-(PA-PB) n , wherein:
PA represents a polymer block comprising one or more units of monomer A and PB represents a branched chain polymer block comprising one or more units of monomer B, with monomer A being a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer, and monomer B being a radically polymerizable triglyceride or mixtures thereof, in the form of a plant oil, animal oil, or synthetic triglycerides; and
n is an integer ranging from 1 to 10,
wherein TCTA is a moiety in the PB block or PA block from a telechelic chain transfer agent used to produce the telechelic thermoplastic block copolymer and wherein said block copolymer has a number average degree of polymerization (N n ) of up to 100,000 without gelation.

3. The thermoplastic block copolymer of claim 1 , wherein the block copolymer has a triblock polymer architecture of PA-PB-PA or PB-PA-PB.

4. The thermoplastic block copolymer of claim 1 , wherein the block copolymer has a pentablock polymer architecture of PA-PB-PA-PB-PA or PB-PA-PB-PA-PB.

5. The thermoplastic block copolymer of claim 1 , wherein the block copolymer has a (PA-PB) n architecture, wherein n is an integer ranging from 1 to 10.

6. The thermoplastic block copolymer of claim 1 , wherein the block copolymer has a (PA-PB) n -PA architecture, wherein n is an integer ranging from 1 to 10.

7. The thermoplastic block copolymer of claim 1 , wherein the block copolymer has a PB-(PA-PB) n architecture, wherein n is an integer ranging from 1 to 10.

8. The thermoplastic block copolymer of claim 1 , wherein the PA block comprises a polymerized linear-chain or branched-chain A monomer, or radicals thereof.

9. The thermoplastic block copolymer of claim 1 , wherein the monomer A is selected from the group consisting of styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, 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.

10. The thermoplastic block copolymer of claim 9 , wherein the monomer A is styrene.

11. The thermoplastic block copolymer of claim 1 , the polymerized triglyceride or mixtures thereof comprises one or more conjugated sites.

12. The thermoplastic block copolymer of claim 11 , wherein the conjugated site is formed by acrylate groups.

13. The thermoplastic block copolymer of claim 11 , wherein the triglyceride is acrylated epoxidized triglyceride.

14. The thermoplastic block copolymer of claim 11 , wherein the triglyceride is:

15. The thermoplastic block copolymer of claim 1 , wherein the PB block is polymerized plant oil or animal oil which is subsequently partially or fully saturated via catalytic hydrogenation post-polymerization.

16. The thermoplastic block copolymer of claim 1 , wherein the monomer B 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.

17. The thermoplastic block copolymer of claim 1 , wherein the block copolymer has a PA-PB-PA triblock polymer architecture, with the PA block being a linear-chain polystyrene or radicals thereof, and the PB block being a branched-chain polymerized vegetable oil or radicals thereof.

18. The thermoplastic block copolymer of claim 17 , wherein the vegetable oil is acrylated epoxidized vegetable oil, wherein the vegetable oil is soybean oil, linseed oil, corn oil, flax seed oil, or rapeseed oil.

19. The thermoplastic block copolymer of claim 17 , wherein the block copolymer has a number average molecular weight ranging from 7 kDa to 10,000 kDa.

20. The thermoplastic block copolymer of claim 17 , wherein the PB block has a glass transition temperature (T g ) below −15° C.

21. The thermoplastic block copolymer of claim 20 , wherein the PB block has a T g ranging from −60° C. to −28° C.

22. The thermoplastic block copolymer of claim 17 , wherein the block copolymer comprises 5 wt % to 95 wt % of PA block and 95 wt % to 5 wt % of PB block.

23. In an elastomeric composition, the improvement comprising the thermoplastic block copolymer of claim 1 .

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

25. In a toughened engineering thermoplastic composition, the improvement comprising the thermoplastic block copolymer of claim 1 .

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

27. The asphalt composition of claim 26 , wherein the asphalt composition comprises 1 to 5 wt % of the thermoplastic block copolymer.

28. The asphalt composition of claim 26 further comprising a bitumen component.

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

30. In a vehicle tire, the improvement comprising the thermoplastic block copolymer of claim 1 .

31. The vehicle tire of claim 30 , wherein the tire is vulcanized, cross-linked, compatibilized, and/or compounded with one or more other material.

32. A method of preparing a thermoplastic block copolymer, said method comprising:
providing a radically polymerizable monomer, represented by A, or a polymer block PA comprising one or more units of monomer A;
providing a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, in the form of a plant or animal oil, represented by B; and
polymerizing monomer A or the polymer block PA with monomer B 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 block copolymer, which includes a branched-chain PB block, wherein said polymerizing is carried out under conditions effective to achieve a number average degree of polymerization (N n ) for

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

• 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

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08L95/00

  Compositions of bituminous materials, e.g. asphalt, tar, pitch · CPC title