Thermoplastic elastomers via atom transfer radical polymerization of plant oil

Patent metadata

Field	Value
Publication number	US-10570238-B2
Application number	US-201815896151-A
Country	US
Kind code	B2
Filing date	Feb 14, 2018
Priority date	Jan 18, 2012
Publication date	Feb 25, 2020
Grant date	Feb 25, 2020

Abstract

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.

First claim

What is claimed:

1. 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 more than one unit of monomer A;
providing a radically polymerizable plant oil monomer containing one or more triglycerides, represented by B; and
radical polymerizing monomer A or the polymer block PA with monomer B, in the presence of an initiator and a transition-metal catalyst system to form the thermoplastic block copolymer.

2. The method of claim 1 , wherein said radical polymerizing comprises:
a) radical polymerizing monomer A in a solvent suitable for dissolving PA; and
b) radical polymerizing monomer B in a solvent suitable for dissolving PA and PB, with PA from step a) being the initiator, to form a diblock copolymer PA-PB.

3. A method of preparing a thermoplastic block copolymer, said method comprising:
providing a radically polymerizable plant oil monomer containing one or more triglycerides, represented by B, or a polymer block PB comprising more than one unit of monomer B;
providing a radically polymerizable monomer, represented by A; and
radical polymerizing monomer B or the polymer block PB with monomer A, in the presence of an initiator and a transition-metal catalyst system, to form the thermoplastic block copolymer.

4. The method of claim 3 , wherein said radical polymerizing comprises:
a) radical polymerizing monomer B in a solvent suitable for dissolving PB; and
b) radical polymerizing monomer A in a solvent suitable for dissolving PA and PB, with PB from step a) as the initiator, to form the diblock copolymer PB-PA.

5. The method of claim 2 , further comprising:
c) radical polymerizing monomer A or monomer B with the formed block copolymer in step b) as the initiator, thereby adding an additional polymer block to the block copolymer formed in step b).

6. The method of claim 5 , further comprising:
d) repeating step c) to form a multiple block copolymer.

7. The method of claim 1 , further comprising:
catalytically hydrogenating the PB block to partial or full saturation after said radical polymerizing.

8. The method of claim 1 , wherein said radical polymerizing is carried out by atom transfer radical polymerization.

9. The method of claim 1 , wherein the monomer A is vinyl, acrylic, diolefin, nitrile, dinitrile, or acrylonitrile monomer.

10. The method 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.

11. The method of claim 10 , wherein the monomer A is styrene.

12. The method of claim 1 , wherein the plant oil is soybean oil, linseed oil, flax seed oil, or rapeseed oil.

13. The method of claim 1 , wherein the plant oil is acrylated epoxidized plant oil.

14. The method of claim 1 , wherein the monomer A is styrene, and the monomer B is soybean oil.

15. The method of claim 1 , wherein said radical polymerizing is carried out at a temperature of 65 to 100° C.

16. The method of claim 2 , wherein said radical polymerizing of step a) forms a PA block having a molecular weight of 1 to 300 kDa.

17. The method of claim 2 , wherein the diblock copolymer PA-PB or PB-PA has a molecular weight of 5 to 500 kDa.

18. The method of claim 5 , wherein said radical polymerizing of step c) forms a block copolymer PA-PB-PA having a molecular weight of 7 to 1000 kDa.

19. The method of claim 2 , wherein the solvent is toluene, THF, chloroform, cyclohexane, or a mixture thereof.

20. The method of claim 19 , wherein the monomer concentration dissolved in the solvent ranges from 5% to 100% weight percentage monomer.

21. The method of claim 1 , wherein the initiator is an aryl halide.

22. The method of claim 21 , wherein the initiator is benzyl chloride.

23. The method of claim 1 , wherein the transition-metal catalyst system comprises a transition-metal compound and a ligand capable of coordinating to the transition metal of the transition-metal compound.

24. The method of claim 23 , wherein the transition-metal compound is CuCl.

25. The method of claim 23 , wherein the ligand is a N-, O-, P-, or S-containing compound capable of coordinating with the transition metal in a form of σ- or π-bond.

26. The method of claim 25 , wherein the ligand is pentamethyldiethylenetriamine (PMDETA).

27. A method of preparing a thermoplastic polymer or polymer block, said method comprising:
providing a radically polymerizable plant oil monomer containing one or more triglycerides; and
radical polymerizing said plant oil monomer, in the presence of an initiator and a transition-metal catalyst system to form the thermoplastic polymer or polymer block.

28. The method of claim 27 , wherein said radical polymerizing is carried out by atom transfer radical polymerization.

29. The method of claim 27 , wherein the plant oil is soybean oil, linseed oil, flax seed oil, or rapeseed oil.

30. The method of claim 27 , wherein the plant oil is acrylated epoxidized plant oil.

31. The method of claim 1 , wherein the method is carried out in the presence of a counter-catalyst and a solvent at a temperature ranging from 65 to 85° C.

Assignees

• Univ Iowa State Res Found Inc

Inventors

• Cochran Eric William
• Williams Ronald Christopher
• Hernandez Nacu
• Cascione Andrew A

Classifications

• 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

• C08L2666/24

  Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof · CPC title

• C08L53/00

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

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08L2555/80

  Macromolecular constituents · CPC title