Apopinene as a biorenewable monomer for ring-opening metathesis polymerization

Patent metadata

Field	Value
Publication number	US-9850340-B2
Application number	US-201615289686-A
Country	US
Kind code	B2
Filing date	Oct 10, 2016
Priority date	Oct 8, 2015
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

Ring-opening metathesis polymerization of apopinene and related functionalized monomers and corresponding polymer products.

First claim

We claim:

1. A method of using a pinene derivative for ring-opening metathesis polymerization, said method comprising:
providing starting material comprising an apopinene monomer component; and
reacting said starting material with a metathesis catalyst component under reaction conditions promoting ring-opening metathesis polymerization of said starting material, to provide a polyalkene product.

2. The method of claim 1 wherein the metal center of said metathesis catalyst component is selected from Re, Ru, Mo or W.

3. The method of claim 2 wherein said metal center is Ru.

4. The method of claim 3 wherein said metathesis catalyst component is selected from Ru-based Grubbs catalysts.

5. The method of claim 4 wherein said metathesis catalyst component is a Grubbs III catalyst.

6. The method of claim 5 wherein said metathesis catalyst component is regioselective for said apopinene monomer component.

7. The method of claim 1 wherein said reacting is carried out is in a solvent.

8. The method of claim 7 wherein said solvent is selected from benzene, dichloromethane or tetrahydrofuran.

9. The method of claim 8 wherein said solvent is tetrahydrofuran.

10. The method of claim 1 wherein said apopinene monomer component is selected from apopinene or apopinene comprising an allylic functional group, wherein said allylic functional group is selected from OH, or RC(O)O, where R is selected from alkyl, substituted alkyl, aryl or substituted aryl moieties, said substituents are selected from hydroxy, amino, halo, C 1 -C 6 alkyl, C 1 -C 6 alkoxy substituents, or combinations thereof.

11. The method of claim 10 wherein R is selected from C 1 -C 6 alkyl or phenyl moieties.

12. The method of claim 1 comprising further reaction of a carbon-carbon double bond of said polyalkene product.

13. The method of claim 12 wherein said further reaction is selected from hydrogenation, halogenation, dihydroxylation, epoxidation, or cross-linkage of said polyalkene product.

14. A method of preparing a polymer of apopinene, said method comprising:
providing a fluid medium comprising an apopinene monomer component;
contacting such a medium with a metathesis catalyst component; and
reacting said apopinene monomer component with said metathesis catalyst component under conditions promoting ring-opening metathesis polymerization, to provide a polyalkene product.

15. The method of claim 14 wherein the metal center of said metathesis catalyst component is selected from Re, Ru, Mo and W.

16. The method of claim 15 wherein said metal center is Ru.

17. The method of claim 16 wherein said metathesis catalyst component is selected from Ru-based Grubbs catalysts.

18. The method of claim 17 wherein said metathesis catalyst component is a Grubbs III catalyst.

19. The method of claim 14 wherein said fluid medium comprises a solvent selected from benzene, dichloromethane or tetrahydrofuran.

20. The method of claim 19 wherein said solvent is tetrahydrofuran.

21. The method of claim 14 wherein said apopinene monomer component is selected from apopinene or apopinene comprising an allylic functional group, wherein said allylic functional group is selected from OH, or RC(O)O, where R is selected from alkyl, substituted alkyl, aryl or substituted aryl moieties, and substituents are selected from hydroxy, amino, halo, C 1 -C 6 alkyl and C 1 -C 6 alkoxy substituents, or combinations thereof.

22. The method of claim 21 wherein R is selected from C 1 -C 6 alkyl or phenyl moieties.

23. The method of claim 14 comprising further reaction of a carbon-carbon double bond of said polyalkene product.

24. The method of claim 23 wherein said further reaction is selected from hydrogenation, halogenation, dihydroxylation, epoxidation, or cross-linkage of said polyalkene product.

25. A polymer comprising a ring-opening polymerization product of an apopinene monomer component, said polymer comprising cis-configured monomeric linkages, trans-configured monomeric linkages and combinations thereof.

26. The polymer of claim 25 wherein said apopinene monomer component is selected from apopinene or apopinene comprising an allylic functional group, wherein said allylic functional group is selected from OH, or RC(O)O, where R is selected from alkyl, substituted alkyl, aryl or substituted aryl moieties, and substituents are selected from hydroxy, amino, halo, C 1 -C 6 alkyl, C 1 -C 6 alkoxy substituents, or combinations thereof.

27. The polymer of claim 25 wherein R is selected from C 1 -C 6 alkyl or phenyl moieties.

28. The polymer of claim 25 wherein a carbon-carbon double bond of said polymer is transformed.

29. The polymer of claim 28 wherein transformation of said polymer is selected from hydrogenation, halogenation, dihydroxylation, epoxidation, or cross-linkage of said polymer.

30. The polymer of claim 25 comprising solely unfunctionalized apopinene monomer components.

31. The polymer of claim 25 wherein all carbon-carbon double bonds have a trans-configuration.

Assignees

• Univ Northwestern

Inventors

• Thomson Regan J
• Strick Benjamin F
• Geiger Franz M
• Delferro Massimiliano

Classifications

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G61/06

  prepared by ring-opening of carbocyclic compounds · CPC title

• C08G2261/3325

  derived from other polycyclic systems · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title