Polymerization of isoprene from renewable resources

• US 8,546,506 B2
• Filed: 06/16/2010
• Issued: 10/01/2013
• Est. Priority Date: 06/17/2009
• Status: Active Grant

• Current Assignee: Goodyear Tire & Rubber Company, Danisco US, Inc. (International Flavors & Fragrances Incorporated)
• Original Assignee: Goodyear Tire & Rubber Company, Danisco US, Inc. (International Flavors & Fragrances Incorporated)
• Inventors: McAuliffe, Joseph C., Paramonov, Sergey, Rodewald, Stephan, Sanford, Karl J.
• Primary Examiner(s): Teskin, Fred M
• Application Number:
  US12/817,093
• Publication Number:
  US 20110040058A1
• Time in Patent Office: 1,203 Days
• Field of Search: 526/75, 526/340.2, 526/337, 526/340, 435/167, 585/18, 524/573, 524/575, 524/856
• US Class Current: 526/337
• 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

The invention features 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 the 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. The present invention more specifically discloses a polyisoprene polymer which is comprised of repeat units that are derived from isoprene monomer, wherein the polyisoprene polymer has δ¹³C value of greater than −22‰. This type of polyisoprene can be a cis-1,4-polyisoprene homopolymer rubber. Also provided are methods for verifying that a polyisoprene homopolymer or a copolymer having repeat units that are derived from isoprene contains isoprene that is from a sustainable renewable non-petroleum derived source.

Claims

1. A system for producing a copolymer of isoprene comprising:

(a) an isoprene starting composition derived from renewable resources, wherein the isoprene starting composition is comprised of greater than about 2 mg of isoprene and one or more compounds selected from the group consisting of ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone 2-methyl-2-vinyloxirane, cis- and trans-3-methyl-1, 3-pentadiene, a C5 prenyl alcohol, 2-heptanone, 6-methyl-5-hepten-2-one, 2,4,5-trimethylpyridine, 2,3,5-trimethylpyrazine, citronellal, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propadol, 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, and (Z)-3,7-dimethyl-1,3,6-octatriene; and

(b) a polymer produced from at least a portion of the isoprene starting material;

wherein at least a portion of the isoprene starting composition undergoes polymerizettion with another non-isoprene molecule to produce a copolymer.

4. The system of claim 1, when in the isoprene starting composition derived from renewable resources comprises less than or about 0.5 μ

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

5. The system of claim 1 wherein the polymer is a copolymer selected from the group consisting of (i) copcilymers of isoprene and 1,3-butadiene, (ii) copolymers of isoprene and styrene, (iii) copolymers of isoprene, 1,3-butadiene, and styrene, and (iv) copolymers of isoprene and α

-methyl styrene.

6. The system of claim 1 wherein the polymer 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.

7. The system of claim 1, further comprising one or more of:

(i) a catalyst for polymerizing isoprene, (ii) a polymerization initiator,(iii) an ionic surfactant, (iv) a suitable organic solvent, and (v) a polymerization chain terminator.

8. The system of claim 1, wherein the isoprene starting composition includes ethanol.

9. The system of claim 1, wherein the isoprene starting composition derived from renewable resources includes acetone.

10. The system of claim 1, wherein the isoprene starting composition derived from renewable resources includes at least one C5 prenyl alcohol.

11. The system of claim 1, wherein the isoprene starting composition derived from renewable resources includes at least one isoprenoid compouhds with 10 or more carbon atoms.

12. The system of claim 1, wherein the polymer is a copolymer selected from the group consisted consisting of (i) copolymers of isoprene and diene monomers, (ii) copolymers of isoprene and conjugated diolefin monomers, and (ii) copolymers of isoprene and ethylenically unsaturated monomers.

2. A system for producing a copolymer of isoprene comprising:

(a) an isoprene starting composition derived from renewable resources; and

(b) a polymer produced from at least a portion of the isoprene starting material., wherein at least a portion of the isoprene starting composition undergoes polymerization with another non-isoprene molecule to produce a copolymer, wherein tie isoprene starting composition derived from renewable resources comprises greater than about 2 mg of isoprene and comprises greater than or about 99.94% isoprene by weight compared to the total weight of all C5 hydrocarbons in the composition.

13. The system of claim 2, wherein the polymer is a copolymer selected from the group consisted consisting of (i) copolymers of isoprene and diene monomers, (ii) copolymers of isoprene and conjugated diolefin monomers, and (iii) copolymers of isoprene and ethylenically unsaturated monomers.

14. The system of claim 2, wherein the polymer is a copolymer selected from the group consisted consisting of (i) copolymers of isoprene and 1,3-butadiene, (ii) copolymers of isoprene and styrene, (iii) copolymers of isoprene, 1,3-butadiene , and styrene, and (iv) copolymers of isoprene and a-methyl styrene.

15. The system of claim 2, wherein the polymer 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 fM value which is greater than 0.9.

16. The system of claim 2, further comprising one or more of:

(i) a catalyst for polymerizing isoprene, (ii) a polymerization initiator, (iii) an ionic surfactant, (iv) a suitable organic solvent, and (v) a polymerization chain terminator.

3. A system for producing a copolymer of isoprene comprising:

(a) an isoprene starting composition derived from renewable resources; and

(b) a polymer produced from at least a portion of the isoprene starting material;

wherein at least a portion of the isoprene startipg composition undergoes polymerization with another non-isoprene molecule to produce a copolymer, wherein the isoprene starting composition derived from renewable resources comprises greater than about 2 mg of isoprene and comprises one or more compounds selected from the group consisting of ethanol, acetone, C5 prenyl alcohols, and isoprenoid compounds with 10 or more carbon atoms.

17. The system of claim 3, wherein the polymer is a copolymer selected from the group consisted consisting of (i) copolymers of isoprene and diem monomers, (ii) copolymers of isoprene and conjugated diolefin monomers, and (iii) copolymers of isoprene and ethylenically unsaturated monomers.

18. The system of claim 3, wherein the polymer is a copolymer selected from the group consisted consisting of (i) copolymers of isoprene and 1,3-butadiene, (ii) copolymers of isoprene and styrene, (iii) copolymers of isoprene, 1,3-butadiene, and styrene, and (iv) copolymers of isoprene and α

-methyl styrene.

19. The system of claim 3, wherein the polymer 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 fM value which is greater than 0.9.

20. The system of claim 3, further comprising bne or more of (i) a catalyst for polymerizing isoprene, (ii) a polymerization initiator, (iii) an ionic surfactant, (iv) a suitable organic solvent, and (v) a polymerization chain terminator.

21. The system of claim 3, wherein the isoprene starting composition derived from renewable resources includes acetone.

22. The system of claim 3, wherein the isoprene starting composition derived from renewable resources includes at least one C5 prenyl alcohol.

23. The system of claim 3, wherein the isoprene starting composition derived from renewable resources includes at least one isoprenoid compounds with 10 or more carbon atoms.