Polymer synthetic technique

• US 8,283,423 B2
• Filed: 09/28/2007
• Issued: 10/09/2012
• Est. Priority Date: 09/29/2006
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Swager, Timothy M., Amara, John P.
• Primary Examiner(s): Teskin, Fred M
• Application Number:
  US12/311,378
• Publication Number:
  US 20100063225A1
• Time in Patent Office: 1,838 Days
• Field of Search: 526/75, 526/284, 526/285, 525/245, 525/328.1, 525/326.1, 525/359.3, 525/417, 525/938
• US Class Current: 526/75
• CPC Class Codes: C07C 41/16 by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
• CPC Class Codes: C07C 41/30 by increasing the number of carbon atoms, e.g. by oligomerisation
• CPC Class Codes: C07C 43/225 containing halogen
• CPC Class Codes: C07C 43/23 containing hydroxy or O-metal groups
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Abstract

The present invention generally relates to methods for the synthesis of species including monomers and polymers. Methods of the invention comprise the use of chemical techniques including metathesis chemistry to synthesize, for example, monomers and/or polymers with desired functional groups.

Claims

1. A method for synthesizing a polymer containing a desired functional group, comprising:

providing a species comprising a carbon-carbon double bond;

performing a metathesis reaction between the species and a functional group precursor to form a covalent bond therebetween, thereby forming a functionalized species; and

polymerizing the functionalized species, with or without other non- or differently-functionalized species, to form a conjugated polymer comprising the functional group.

2. A method as in claim 1, wherein performing the metathesis reaction comprises exposing the species and the functional group precursor to a metathesis catalyst comprising ruthenium, molybdenum, or tungsten.

3. A method as in claim 1, wherein the metathesis reaction is a cross-metathesis, a ring-closing metathesis, or a ring-opening metathesis reaction.

4. A method as in claim 1, wherein polymerizing the functionalized species comprises cationic polymerization, anionic polymerization, radical polymerization, condensation polymerization, Wittig polymerization, ring-opening polymerization, cross-coupling polymerization, addition polymerization, or chain polymerization.

5. A method as in claim 1, wherein the functional group precursor comprises a carbon-carbon double bond and the functional group.

6. A method as in claim 1, wherein the functional group precursor comprises alkyl, alkene, alkyne, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, hydroxy, carbonyl groups, nitro, nitroso, peroxide, cyano, isocyano, amino, halogen, azo, cyanate, isocyanate, ether, acetal, imine, alkoxy, phosphine, phosphate, phosphodiester, phosphonic acid, phosphinic acid, sulfide, sulfone, sulfonic acid, sulfoxide, thiol, metal complex, substituted derivatives thereof, or combinations thereof.

7. A method as in claim 1, wherein the polymer is a homopolymer, a random copolymer, a block co-polymer, or a biological polymer.

8. A method as in claim 1, wherein the polymer comprises a pendant group comprising the functional group.

9. A method as in claim 1, wherein the metathesis reaction is performed at a temperature of 100°

C. or less.

10. A method as in claim 1, wherein the metathesis reaction is performed at a temperature of 75°

C. or less.

11. A method as in claim 1, wherein the metathesis reaction is performed at a temperature of 50°

C. or less.

12. A method as in claim 1, wherein the metathesis reaction is performed at a temperature of 25°

C. or less.

13. A method for synthesizing a polymer containing a desired functional group, comprising:

providing a polymer comprising at least one carbon-carbon double bond; and

performing a metathesis reaction between the polymer and a functional group precursor such that a covalent bond is formed therebetween, thereby forming a conjugated polymer comprising the functional group.

14. A method as in claim 13, wherein performing the metathesis reaction comprises exposing the polymer and the functional group precursor to a catalyst comprising ruthenium, molybdenum, or tungsten.

15. A method as in claim 13, wherein the metathesis reaction is a cross-metathesis, a ring-closing metathesis, or a ring-opening metathesis reaction.

16. A method as in claim 13, wherein the polymer comprising at least one carbon-carbon double bond comprises a pendant group comprising the carbon-carbon double bond.

17. A method as in claim 13, wherein the functional group precursor comprises a carbon-carbon double bond and the functional group.

18. A method as in claim 13, wherein the functional group precursor comprises alkyl, alkene, alkyne, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, hydroxy, carbonyl groups, nitro, nitroso, peroxide, cyano, isocyano, amino, halogen, azo, cyanate, isocyanate, ether, acetal, imine, alkoxy, phosphine, phosphate, phosphodiester, phosphonic acid, phosphinic acid, sulfide, sulfone, sulfonic acid, sulfoxide, thiol, metal complex, substituted derivatives thereof, or combinations thereof.

19. A method as in claim 13, wherein the polymer is a homopolymer, a random copolymer, a block co-polymer, or a biological polymer.

20. A method as in claim 13, wherein the metathesis reaction is performed at a temperature of 100°

C. or less.

21. A method as in claim 13, wherein the metathesis reaction is performed at a temperature of 75°

C. or less.

22. A method as in claim 13, wherein the metathesis reaction is performed at a temperature of 50°

C. or less.

23. A method as in claim 13, wherein the metathesis reaction is performed at a temperature of 25°

C. or less.

24. A method for synthesizing a polymer containing a desired functional group, comprising:

providing a polymer comprising at least one carbon-carbon double bond; and

performing a metathesis reaction between the polymer and a functional group precursor such that a covalent bond is formed therebetween, thereby forming a conjugated polymer comprising a pendant group comprising the functional group.

25. A method as in claim 24, wherein performing the metathesis reaction comprises exposing the polymer and the functional group precursor to a catalyst comprising ruthenium, molybdenum, or tungsten.

26. A method as in claim 24, wherein the metathesis reaction is a cross-metathesis, a ring-closing metathesis, or a ring-opening metathesis reaction.

27. A method as in claim 24, wherein the polymer comprising at least one carbon-carbon double bond comprises a pendant group comprising the carbon-carbon double bond.

28. A method as in claim 24, wherein the functional group precursor comprises a carbon-carbon double bond and the functional group.

29. A method as in claim 24, wherein the functional group precursor comprises alkyl, alkene, alkyne, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, hydroxy, carbonyl groups, nitro, nitroso, peroxide, cyano, isocyano, amino, halogen, azo, cyanate, isocyanate, ether, acetal, imine, alkoxy, phosphine, phosphate, phosphodiester, phosphonic acid, phosphinic acid, sulfide, sulfone, sulfonic acid, sulfoxide, thiol, metal complex, substituted derivatives thereof, or combinations thereof.

30. A method as in claim 24, wherein the polymer is a homopolymer, a random copolymer, a block co-polymer, or a biological polymer.

31. A method as in claim 24, wherein the metathesis reaction is performed at a temperature of 100°

C. or less.

32. A method as in claim 24, wherein the metathesis reaction is performed at a temperature of 75°

C. or less.

33. A method as in claim 24, wherein the metathesis reaction is performed at a temperature of 50°

C. or less.

34. A method as in claim 24, wherein the metathesis reaction is performed at a temperature of 25°

C. or less.

35. A method for synthesizing a polymer containing a desired functional group, comprising:

providing a polymer comprising at least one pendant group comprising a carbon-carbon double bond; and

performing a metathesis reaction between the polymer and a functional group precursor such that a covalent bond is formed therebetween, thereby forming a conjugated polymer comprising the functional group.

36. A method as in claim 35, wherein performing the metathesis reaction comprises exposing the polymer and the functional group precursor to a catalyst comprising ruthenium, molybdenum, or tungsten.

37. A method as in claim 35, wherein the metathesis reaction is a cross-metathesis, a ring-closing metathesis, or a ring-opening metathesis reaction.

38. A method as in claim 35, wherein the functional group precursor comprises a carbon-carbon double bond and the functional group.

39. A method as in claim 35, wherein the functional group precursor comprises alkyl, alkene, alkyne, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, hydroxy, carbonyl groups, nitro, nitroso, peroxide, cyano, isocyano, amino, halogen, azo, cyanate, isocyanate, ether, acetal, imine, alkoxy, phosphine, phosphate, phosphodiester, phosphonic acid, phosphinic acid, sulfide, sulfone, sulfonic acid, sulfoxide, thiol, metal complex, substituted derivatives thereof, or combinations thereof.

40. A method as in claim 35, wherein the polymer is a homopolymer, a random copolymer, a block co-polymer, or a biological polymer.

41. A method as in claim 35, wherein the polymer comprises a pendant group comprising the functional group.

42. A method as in claim 35, wherein the metathesis reaction is performed at a temperature of 100°

C. or less.

43. A method as in claim 35, wherein the metathesis reaction is performed at a temperature of 75°

C. or less.

44. A method as in claim 35, wherein the metathesis reaction is performed at a temperature of 50°

C. or less.

45. A method as in claim 35, wherein the metathesis reaction is performed at a temperature of 25°

C. or less.