Thermoplastic elastomers via atom transfer radical polymerization of plant oil
The present invention relates to a 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, or acrylonitrile monomer. Monomer B is a radically polymerizable plant oil monomer containing one or more triglycerides. The present invention also relates to a method of preparing a thermoplastic block copolymer by radical polymerizing a radically polymerizable monomer with a radically polymerizable plant oil monomer containing one or more triglycerides, in the presence of an initiator and a transition-metal catalyst system to form the thermoplastic block copolymer. The polymerized plant oil-based block copolymers are useful in a variety of applications, such as asphalt modifiers, rubber compositions, adhesives, tires, in the automobile industry, footwear, packaging, etc.
1. A thermoplastic block copolymer comprising at least one PA block and at least one PB block, wherein PA represents a polymer block comprising more than one unit of monomer A and PB represents a branched-chain polymer block comprising more than one unit of monomer B, with monomer A being a vinyl, acrylic, diolefin, nitrile, dinitrile, or acrylonitrile monomer, and monomer B being a radically polymerizable plant oil monomer containing one or more triglycerides.
2. The thermoplastic block copolymer of claim 1 , wherein the thermoplastic block copolymer has a triblock polymer architecture of PA-PB-PA or PB-PA-PB.
3. The thermoplastic block copolymer of claim 1 , wherein the thermoplastic block copolymer has a pentablock polymer architecture of PA-PB-PA-PB-PA or PB-PA-PB-PA-PB.
4. The thermoplastic block copolymer of claim 1 , wherein the thermoplastic block copolymer has a (PA-PB) n architecture, wherein n is an integer ranging from 2 to 10.
5. The thermoplastic block copolymer of claim 1 , wherein the thermoplastic block copolymer has a (PA-PB) n -PA architecture, wherein n is an integer ranging from 2 to 10.
6. The thermoplastic block copolymer of claim 1 , wherein the thermoplastic block copolymer has a PB-(PA-PB) n architecture, wherein n is an integer ranging from 2 to 10.
7. The thermoplastic block copolymer of claim 1 , wherein the PA block comprises repeating units of monomer A and the PB block comprises repeating units of monomer B.
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, a-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 , wherein the PB block comprises polymerized triglyceride or mixtures thereof.
12. The thermoplastic block copolymer of claim 11 , wherein the polymerized triglyceride or mixtures thereof comprises one or more conjugated sites.
13. The thermoplastic block copolymer of claim 12 , wherein the conjugated site is formed by acrylate groups.
14. The thermoplastic block copolymer of claim 11 , wherein the triglyceride is acrylated epoxidized triglyceride.
15. The thermoplastic block copolymer of claim 11 , wherein the triglyceride is:
16. The thermoplastic block copolymer of claim 1 , wherein the PB block is polymerized plant oil which is subsequently partially or fully saturated via catalytic hydrogenation post-polymerization.
17. The thermoplastic block copolymer of claim 1 , wherein the plant oil is soybean oil, linseed oil, flax seed oil, or rapeseed oil.
18. The thermoplastic block copolymer of claim 1 , wherein the thermoplastic 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 linear-chain or branched-chain polymerized soybean oil or radicals thereof.
19. The thermoplastic block copolymer of claim 18 , wherein the soybean oil is acrylated epoxidized soybean oil.
20. The thermoplastic block copolymer of claim 18 , wherein the thermoplastic block copolymer has a number averaged molecular weight ranging from 7 kDa to 1000 kDa.
21. The thermoplastic block copolymer of claim 18 , wherein the PB block has a glass transition temperature (T g ) below −15° C.
22. The thermoplastic block copolymer of claim 21 , wherein the PB block has a T g ranging from −60° C. to −28° C.
23. The thermoplastic block copolymer of claim 18 , wherein the thermoplastic block copolymer comprises 5 wt % to 95 wt % of PA block and 95 wt % to 5 wt % of PB block.
24. In an elastomeric composition, the improvement comprising the thermoplastic block copolymer of claim 1 .
25. An elastomeric composition comprising the block copolymer of claim 1 , wherein the thermoplastic block copolymer is vulcanized, cross-linked, compatibilized, and/or compounded with one or more other elastomer, additive, modifier and/or filler.
26. In a toughened engineering thermoplastic composition, the improvement comprising the thermoplastic block copolymer of claim 1 .
27. In an asphalt composition, the improvement comprising the thermoplastic block copolymer of claim 1 as an asphalt additive, modifier, and/or filler.
28. The asphalt composition of claim 27 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 thermoplastic polymer comprising more than one unit of a radically polymerizable conjugated plant oil monomer containing one or more conjugated triglycerides, said thermoplastic polymer being prepared by radical polymerization with a halide initiator.
33. The thermoplastic polymer of claim 32 , wherein the thermoplastic polymer comprises a polymerized linear-chain or branched-chain plant oil, or radicals thereof.
34. The thermoplastic polymer of claim 32 , wherein the plant oil is soybean oil, linseed oil, flax seed oil, or rapeseed oil.
35. The thermoplastic polymer of claim 32 , wherein the plant oil is acrylated epoxidized plant oil.
36. The asphalt composition of claim 27 , wherein the asphalt composition comprises 1 to 5 wt % of the thermoplastic block copolymer.
37. A thermoplastic, branched chain polymer comprising more than one unit of a radically polymerizable plant oil monomer containing one or more triglycerides, said thermoplastic polymer being prepared by radical polymerization with a halide initiator.