Polymerization of isoprene from renewable resources

• US 8,901,262 B2
• Filed: 08/20/2013
• Issued: 12/02/2014
• Est. Priority Date: 06/17/2009
• Status: Active Grant

• Current Assignee: Goodyear Tire & Rubber Company, Danisco USA Incorporated (International Flavors & Fragrances Incorporated)
• Original Assignee: Goodyear Tire & Rubber Company, Danisco USA Incorporated (International Flavors & Fragrances Incorporated)
• Inventors: McAuliffe, Joseph C., Paramonov, Sergey, Rodewald, Stephan, Sanford, Karl J.
• Primary Examiner(s): Teskin, Fred M
• Application Number:
  US13/971,484
• Publication Number:
  US 20140080983A1
• Time in Patent Office: 469 Days
• Field of Search: 526/75, 526/337, 526/340, 526/340.2, 526/159, 526/173, 435/167, 524/856
• US Class Current: 526/159
• CPC Class Codes: C08F 36/08 Isoprene
• CPC Class Codes: C08F 4/16 of silicon, germanium, tin, lead, titanium, zirconium or hafnium
• CPC Class Codes: C08F 4/52 selected from boron, aluminium, gallium, indium, thallium or rare earths C08F4/14 takes precedence
• CPC Class Codes: C12P 5/007 containing one or more isoprene units, i.e. terpenes carotenes C12P23/00
• CPC Class Codes: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

This invention relates to compositions and methods for producing polymers of isoprene derived from renewable resources, such as isoprene produced from cultured cells that use renewable carbon sources. A starting isoprene composition, such as a bioisoprene composition, is distinguished from petroleum based isoprene by its purity profile (such as lower levels of certain C₅ hydrocarbons other than isoprene, presence of certain compounds associated with the biological process for production) and the relative content of the carbon isotopes. Polymers obtained by polymerization of such starting isoprene composition according to this invention, such as a polyisoprene homopolymer or a copolymer having repeat units that are derived from isoprene, are distinguishable from isoprene containing polymers from petrochemical resources.

Claims

1. A method for producing polyisoprene derived from renewable resources comprising:

(a) initiating polymerization of isoprene monomer in an isoprene starting composition which is derived from renewable resources, wherein the isoprene starting composition derived from renewable resources comprises greater than about 2 mg of the isoprene monomer and comprises one or more compounds selected from the group consisting of ethanol, acetone, C5 prenyl alcohols, isoprenoid compounds with 10 or more carbon atoms, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 2-methyl-2-vinyloxirane, cis- and trans-3-methyl-1,3-pentadiene, 2-heptanone, 6-methyl-5-hepten-2-one, 2,4,5-trimethylpyridine, 2,3,5-trimethylpyrazine, citronellal, acetaldehyde, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl-1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methylbutyl acetate, 3-methyl-3-buten-1-yl acetate, 3-methyl-2-buten-1-yl acetate, (E)-3,7-dimethyl-1,3,6-octatriene, (Z)-3,7-dimethyl-1,3,6-octatriene, and 2,3-cycloheptenolpyridine;

(b) allowing the polymerization of the isoprene monomer to continue to produce the polyisoprene;

(c) terminating the polymerization of the isoprene monomer, and (d) recovering the polyisoprene.

2. The method of claim 1, wherein the isoprene starting composition derived from renewable resources comprises greater than or about 99.94% isoprene by weight compared to the total weight of all C5 hydrocarbons in the composition.

3. The method of claim 1, wherein the isoprene starting composition derived from renewable resources comprises less than or about 0.5 μ

g/L per compound for any compound in the composition that inhibits the polymerization of isoprene.

4. The method of claim 1 wherein the polyisoprene produced from the isoprene starting material is a polyisoprene polymer which is comprised of repeat units that are derived from isoprene monomer, wherein the polyisoprene polymer has f_M value which is greater than 0.9.

5. The method of claim 1 wherein the polymerization is a solution polymerization which is initiated with an anionic initiator.

6. The method of claim 5 wherein the anionic initiator is an alkyl lithium compound containing from 1 to 8 carbon atoms.

7. The method of claim 6 wherein the polymerization is conducted in the presence of a polar modifier.

8. The method of claim 1 wherein the polymerization is allowed to continue until a conversion of at least about 85 percent is attained.

9. The method of claim 1 wherein the polymerization is initiated with a Ziegler Natta catalyst system.

10. The method of claim 9 wherein the Ziegler Natta catalyst system is comprised of titanium tetrachloride and triethyl aluminum.

11. A method for producing a copolymer of isoprene derived from renewable resources comprising:

(a) initiating copolymerization of isoprene monomer with a non-isoprene molecule in an isoprene starting composition which is derived from renewable resources, wherein the isoprene starting composition derived from renewable resources comprises greater than about 2 mg of the isoprene monomer, at least one non-isoprene molecule, and one or more compounds selected from the group consisting of ethanol, acetone, C5 prenyl alcohols, isoprenoid compounds with 10 or more carbon atoms, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 2-methyl-2-vinyloxirane, cis- and trans-3-methyl-1,3-pentadiene, 2-heptanone, 6-methyl-5-hepten-2-one, 2,4,5-trimethylpyridine, 2,3,5-trimethylpyrazine, citronellal, acetaldehyde, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl-1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methylbutyl acetate, 3-methyl-3-buten-1-yl acetate, 3-methyl-2-buten-1-yl acetate, (E)-3,7-dimethyl-1,3,6-octatriene, (Z)-3,7-dimethyl-1,3,6-octatriene, and 2,3-cycloheptenolpyridine;

(b) allowing the copolymerization of the isoprene monomer and the non-isoprene molecule to continue to produce the copolymer of isoprene;

(c) terminating the copolymerization of the isoprene monomer and the non-isoprene molecule, and (d) recovering the copolymer of isoprene.

12. The method of claim 11, wherein the isoprene starting composition derived from renewable resources comprises greater than or about 99.94% isoprene by weight compared to the total weight of all C5 hydrocarbons in the composition.

13. The method of claim 11, wherein the isoprene starting composition derived from renewable resources comprises less than or about 0.5 μ

g/L per compound for any compound in the composition that inhibits the polymerization of isoprene.

14. The method of claim 11 wherein the non-isoprene molecule is 1,3-butadiene.

15. The method of claim 11 wherein the non-isoprene molecule is styrene.

16. The method of claim 11 wherein the polymerization is a solution polymerization which is initiated with an anionic initiator.

17. The method of claim 16 wherein the anionic initiator is an alkyl lithium compound containing from 1 to 8 carbon atoms.

18. The method of claim 17 wherein the polymerization is conducted in the presence of a polar modifier.

19. The method of claim 11 wherein the polymerization is allowed to continue until a conversion of at least about 85 percent is attained.

20. The method of claim 11 wherein the polymerization is initiated with a Ziegler Nana catalyst system.