FARNESENE INTERPOLYMERS

• US 20100056714A1
• Filed: 09/01/2009
• Published: 03/04/2010
• Est. Priority Date: 09/04/2008
• Status: Active Grant

• Current Assignee: Amyris Inc.
• Original Assignee: Amyris Biotechnologies, Inc.
• Inventors: MCPHEE, Derek James
• Granted Patent: US 8,217,128 B2
• Time in Patent Office: Days
• US Class Current: 524/579
• CPC Class Codes: C08C 19/02 Hydrogenation
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 297/02 using a catalyst of the anionic type
• CPC Class Codes: C08F 36/22 the radical having three or more carbon-to-carbon double bonds
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 47/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 53/005 Modified block copolymers
• CPC Class Codes: C08L 71/12 Polyphenylene oxides
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: Y10T 428/139 Open-ended, self-supporting conduit, cylinder, or tube-type article

Abstract

Farnesene interpolymer comprises units derived from a farnesene (e.g., α-farnesene or β-farnesene) and units derived from at least one vinyl monomer. The farnesene interpolymer can be prepared by copolymerizing the farnesene and at least one vinyl monomer in the presence of a catalyst. In some embodiments, the farnesene is prepared from a sugar by using a microorganism. In other embodiments, the at least one vinyl monomer is ethylene, an α-olefin, or a substituted or unsubstituted vinyl halide, vinyl ether, acrylonitrile, acrylic ester, methacrylic ester, acrylamide or methacrylamide, or a combination thereof.

Claims

1. A farnesene interpolymer comprising one or more polymer molecules having formula (X′

);



X

_n

Y

_m  

 

(X′

),

wherein each of n and m is independently an integer from 1 to about 100,000;

X has one or more of formulae (I′

)-(VIII′

);

and

Y has formula (IX′

);

wherein R¹ has formula (XI);

and

R² has formula (XII);

R³ has formula (XIII);

and

R⁴ has formula (XIV);

wherein each of R⁴, R⁵, R⁶ and R⁷ is independently H, hydrocarbyl, substituted hydrocarbyl, heterocyclyl, substituted heterocyclyl or a functional group containing O, N, S, P or a combination thereof, and wherein the mole percent ratio of X to Y is from about 1;

4 to about 100;

1.

2. The farnesene interpolymer of claim 1, wherein each of R⁴, R⁵, R⁶ and R⁷is H.

3. The farnesene interpolymer of claim 1, wherein one of R⁴ , R⁵, R⁶ and R⁷ is hydrocarbyl;

and each of the other three of R⁴, R⁵, R⁶ and R⁷ is H.

4. The farnesene interpolymer of claim 3, wherein the hydrocarbyl is alkyl, cycloalkyl or aryl.

5. The farnesene interpolymer of claim 1, wherein at least one of R⁴ , R⁵, R⁶ and R⁷ is a functional group.

6. The farnesene interpolymer of claim 5, wherein the functional group is alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile, or halo.

7. The farnesene interpolymer of claim 1, wherein the amount of formula (I′

) is at most about 80 wt. %, based on the total weight of the polyfarnesene.

8. The farnesene interpolymer of claim 1, wherein the amount of formula (II′

) is from about 15 wt. % to about 99 wt. %, based on the total weight of the polyfarnesene.

9. The farnesene interpolymer of claim 1, wherein the farnesene interpolymer is a random interpolymer.

10. The farnesene interpolymer of claim 1, wherein the farnesene interpolymer is a block interpolymer.

34. A polymer composition comprising the farnesene interpolymer of claim 1;

and at least an additive.

35. The polymer composition of claim 34, wherein the additive is a filler, grafting initiator, tackifier, slip agent, anti-blocking agent, plasticizer, antioxidant, blowing agent, blowing agent activator, UV stabilizer, acid scavenger, colorant or pigment, coagent, lubricant, antifogging agent, flow aid, processing aid, extrusion aid, coupling agent, cross-linking agent, stability control agent, nucleating agent, surfactant, flame retardant, antistatic agent, a combination thereof.

36. The polymer composition of claim 34, wherein the additive is a filler.

37. The polymer composition of claim 34, wherein the additive is a cross-linking agent.

38. The polymer composition of claim 34, further comprising a second polymer.

39. The polymer composition of claim 38, wherein the ratio of the farnesene interpolymer to the second polymer is from about 1:

99 to about 99;

1.

40. The polymer composition of claim 38, wherein the second polymer is a polyolefin, polyurethane, polyester, polyamide, styrenic polymer, phenolic resin, polyacrylate, polymethacrylate or a combination thereof.

41. An article comprising the farnesene interpolymer of claim 1.

42. The article of claim 41, wherein the article is a molded article, film, sheet or foam.

43. The article of claim 41, wherein the article is a molded article selected from toys, grips, soft touch handles, bumper rub strips, floorings, auto floor mats, wheels, casters, furniture and appliance feet, tags, seals, gaskets such as static and dynamic gaskets, automotive doors, bumper fascia, grill components, rocker panels, hoses, linings, office supplies, seals, liners, diaphragms, tubes, lids, stoppers, plunger tips, delivery systems, kitchen wares, shoes, shoe bladders, and shoe soles.

11. A method of making a farnesene interpolymer comprising copolymerizing a farnesene and at least one vinyl monomer in the presence of a catalyst, wherein the mole percent ratio of the farnesene to the vinyl monomer is from about 1:

4 to about 100;

1.

12. The method of claim 11, wherein the at least one vinyl monomer does not comprise a terpene.

13. The method of claim 11, wherein the farnesene is α

-farnesene or β

-farnesene or a combination thereof.

14. The method of claim 11, wherein the farnesene is prepared by a microorganism.

15. The method of claim 11, wherein the farnesene is derived from a simple sugar.

16. The method of claim 11, wherein the at least one vinyl monomer is ethylene, an α

-olefin, a substituted or unsubstituted vinyl halide, vinyl ether, acrylonitrile, acrylic ester, methacrylic ester, acrylamide or methacrylamide or a combination thereof.

17. The method of claim 11, wherein the at least one vinyl monomer is styrene.

18. The method of claim 11, wherein the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, an organolithium reagent or a combination thereof.

19. The method of claim 11, wherein the catalyst is an organolithium reagent.

20. The method of claim 19, wherein the catalyst further comprises 1,2-bis(dimethylamino)ethane.

21. The method of claim 19, wherein the organolithium reagent is n-butyl lithium or sec-butyl lithium.

32. A farnesene interpolymer prepared by the method of claim 11.

22. A method of making a farnesene interpolymer comprising:

(a) making a farnesene from a simple sugar by a microorganism; and

(b) copolymerizing the farnesene and at least one vinyl monomer in the presence of a catalyst.

23. The method of claim 22, wherein the mole percent ratio of the farnesene to the vinyl monomer is from about 1:

4 to about 100;

1.

24. The method of claim 22, wherein at least one vinyl monomer does not comprise a terpene.

25. The method of claim 22, wherein the at least one vinyl monomer is ethylene, an α

-olefin, or a substituted or unsubstituted vinyl halide, vinyl ether, acrylonitrile, acrylic ester, methacrylic ester, acrylamide or methacrylamide, or a combination thereof.

26. The method of claim 22, wherein the at least one vinyl monomer is ethylene, an α

-olefin or a combination thereof.

27. The method of claim 22, wherein the at least one vinyl monomer is styrene.

28. The method of claim 22, wherein the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, an organolithium reagent or a combination thereof.

29. The method of claim 22, wherein the catalyst is an organolithium reagent.

30. The method of claim 29, wherein the catalyst further comprises 1,2-bis(dimethylamino)ethane.

31. The method of claim 29, wherein the organolithium reagent is n-butyl lithium or sec-butyl lithium.

33. A farnesene interpolymer prepared by the method of claim 22.