Polymerization Process

• US 20070197753A1
• Filed: 06/20/2005
• Published: 08/23/2007
• Est. Priority Date: 06/21/2004
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Jiang, Peijun, Shirodkar, Pradeep, Speed, Charles, Shutt, John, Hagerty, Robert
• Granted Patent: US 7,981,984 B2
• Time in Patent Office: Days
• US Class Current: 526/348.2
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 2/14 Organic medium
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 4/6493 containing halogen
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

This invention relates to a process to polymerize olefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorocarbon at a temperature above the onset melting point of the polymer. This invention also relates to a solution process to polymerize olefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorocarbon at a temperature above the onset melting point of the polymer.

Claims

1. A process to produce polyolefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorinated hydrocarbon at a polymerization temperature above the onset melting point of the wet polymer, provided that if the polymer does not have an onset melting point, then the polymerization temperature is 70°

C. or more, wherein the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the total volume of fluorocarbons, any hydrocarbon solvents present and any unreacted monomer.

3. The process of claim 1 wherein the polymerization temperature is above 100°

C.

4. The process of claim 1 wherein the polymerization temperature is above 120°

C.

5. The process of claim 1 wherein the polymerization temperature is between 100 and 250°

C.

6. The process of claim 1 wherein the polymerization effluent comprises a hydrocarbon solvent or diluent.

7. The process of claim 6 wherein the hydrocarbon solvent or diluent is selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, octane, isooctane, and cyclohexane.

8. The process of claim 1 where the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the volume of the polymerization medium.

9. The process of claim 1 wherein the fluorinated hydrocarbon comprises a perfluorinated hydrocarbon.

10. The process of claim 1 wherein the fluorinated hydrocarbon comprises a hydrofluorocarbon.

11. The process of claim 1 wherein the fluorinated hydrocarbon is represented by the formula:

C_xH_yF_z wherein x is an integer from 1 to 40, y is an integer greater than or equal to 0 and z is an integer and is at least one.

12. The process of claim 1 wherein the fluorinated hydrocarbon is selected from the group consisting of fluoromethane;

difluoromethane;

trifluoromethane;

fluoroethane;

1,1-difluoroethane;

1,2-difluoroethane;

1,1,1-trifluoroethane;

1,1,2-trifluoroethane;

1,1,1,2-tetrafluoroethane;

1,1,2,2-tetrafluoroethane;

1,1,1,2,2-pentafluoroethane;

1-fluoropropane;

2-fluoropropane;

1,1-difluoropropane;

1,2-difluoropropane;

1,3-difluoropropane;

2,2-difluoropropane;

1,1,1-trifluoropropane;

1,1,2-trifluoropropane;

1,1,3-trifluoropropane;

1,2,2-trifluoropropane;

1,2,3-trifluoropropane;

1,1,1,2-tetrafluoropropane;

1,1,1,3-tetrafluoropropane;

1,1,2,2-tetrafluoropropane;

1,1,2,3-tetrafluoropropane;

1,1,3,3-tetrafluoropropane;

1,2,2,3-tetrafluoropropane;

1,1,1,2,2-pentafluoropropane;

1,1,1,2,3-pentafluoropropane;

1,1,1,3,3-pentafluoropropane;

1,1,2,2,3-pentafluoropropane;

1,1,2,3,3-pentafluoropropane;

1,1,1,2,2,3-hexafluoropropane;

1,1,1,2,3,3-hexafluoropropane;

1,1,1,3,3,3-hexafluoropropane;

1,1,1,2,2,3,3-heptafluoropropane;

1,1,1,2,3,3,3-heptafluoropropane;

1-fluorobutane;

2-fluorobutane;

1,1-difluorobutane;

1,2-difluorobutane;

1,3-difluorobutane;

1,4-difluorobutane;

2,2-difluorobutane;

2,3-difluorobutane;

1,1,1-trifluorobutane;

1,1,2-trifluorobutane;

1,1,3-trifluorobutane;

1,1,4-trifluorobutane;

1,2,2-trifluorobutane;

1,2,3-trifluorobutane;

1,3,3-trifluorobutane;

2,2,3-trifluorobutane;

1,1,1,2-tetrafluorobutane;

1,1,1,3-tetrafluorobutane;

1,1,1,4-tetrafluorobutane;

1,1,2,2-tetrafluorobutane;

1,1,2,3-tetrafluorobutane;

1,1,2,4-tetrafluorobutane;

1,1,3,3-tetrafluorobutane;

1,1,3,4-tetrafluorobutane;

1,1,4,4-tetrafluorobutane;

1,2,2,3-tetrafluorobutane;

1,2,2,4-tetrafluorobutane;

1,2,3,3-tetrafluorobutane;

1,2,3,4-tetrafluorobutane;

2,2,3,3-tetrafluorobutane;

1,1,1,2,2-pentafluorobutane;

1,1,1,2,3-pentafluorobutane;

1,1,1,2,4-pentafluorobutane;

1,1,1,3,3-pentafluorobutane;

1,1,1,3,4-pentafluorobutane;

1,1,1,4,4-pentafluorobutane;

1,1,2,2,3-pentafluorobutane;

1,1,2,2,4-pentafluorobutane;

1,1,2,3,3-pentafluorobutane;

1,1,2,4,4-pentafluorobutane;

1,1,3,3,4-pentafluorobutane;

1,2,2,3,3-pentafluorobutane;

1,2,2,3,4-pentafluorobutane;

1,1,1,2,2,3-hexafluorobutane;

1,1,1,2,2,4-hexafluorobutane;

1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;

1,1,1,2,4,4-hexafluorobutane;

1,1,1,3,3,4-hexafluorobutane;

1,1,1,3,4,4-hexafluorobutane;

1,1,1,4,4,4-hexafluorobutane;

1,1,2,2,3,3-hexafluorobutane;

1,1,2,2,3,4-hexafluorobutane;

1,1,2,2,4,4-hexafluorobutane;

1,1,2,3,3,4-hexafluorobutane;

1,1,2,3,4,4-hexafluorobutane;

1,2,2,3,3,4-hexafluorobutane;

1,1,1,2,2,3,3-heptafluorobutane;

1,1,1,2,2,4,4-heptafluorobutane;

1,1,1,2,2,3,4-heptafluorobutane;

1,1,1,2,3,3,4-heptafluorobutane;

1,1,1,2,3,4,4-heptafluorobutane;

1,1,1,2,4,4,4-heptafluorobutane;

1,1,1,3,3,4,4-heptafluorobutane;

1,1,1,2,2,3,3,4-octafluorobutane;

1,1,1,2,2,3,4,4-octafluorobutane;

1,1,1,2,3,3,4,4-octafluorobutane;

1,1,1,2,2,4,4,4-octafluorobutane;

1,1,1,2,3,4,4,4-octafluorobutane;

1,1,1,2,2,3,3,4,4-nonafluorobutane;

1,1,1,2,2,3,4,4,4-nonafluorobutane;

1-fluoro-2-methylpropane;

1,1-difluoro-2-methylpropane;

1,3-difluoro-2-methylpropane;

1,1,1-trifluoro-2-methylpropane;

1,1,3-trifluoro-2-methylpropane;

1,3-difluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-methylpropane;

1,1,3-trifluoro-2-(fluoromethyl)propane;

1,1,1,3,3-pentafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-(fluoromethyl)propane;

fluorocyclobutane;

1,1-difluorocyclobutane;

1,2-difluorocyclobutane;

1,3-difluorocyclobutane;

1,1,2-trifluorocyclobutane;

1,1,3-trifluorocyclobutane;

1,2,3-trifluorocyclobutane;

1,1,2,2-tetrafluorocyclobutane;

1,1,3,3-tetrafluorocyclobutane;

1,1,2,2,3-pentafluorocyclobutane;

1,1,2,3,3-pentafluorocyclobutane;

1,1,2,2,3,3-hexafluorocyclobutane;

1,1,2,2,3,4-hexafluorocyclobutane;

1,1,2,3,3,4-hexafluorocyclobutane; and

1,1,2,2,3,3,4-heptafluorocyclobutane.

13. The process of claim 1 wherein the fluorinated hydrocarbon is selected from the group consisting of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane, and 1,1,1,2-tetrafluoroethane.

14. The process of claim 12claim 1 wherein the fluorinated hydrocarbon is selected from the group consisting of 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, octafluorocyclobutane, and 2,3-dihydrodecafluoropentane.

15. The process of claim 1 wherein the polymerization medium comprises ethylene.

16. The process of claim 1 where the polymerization medium comprises propylene.

17. The process of claim 1 where the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.

18. The process of claim 1 wherein the polymerization further comprises a hydrocarbon and the fluorinated hydrocarbon is soluble in the hydrocarbon.

19. The process of claim 1 where the fluorinated hydrocarbon is present at 20 to 90 volume %, based upon the volume of the polymerization medium.

20. The process of claim 1 wherein the fluorinated hydrocarbon is present at least 1 weight % based upon the weight of the fluorinated hydrocarbon and any hydrocarbon solvent or diluent present, and where the process further comprises recovering a polymer having an Mw of 70,000 or more and a percent crystallinity of 20% or more.

21. The process of claim 1 further comprising introducing a fluorinated hydrocarbon into the polymer effluent.

22. The process of claim 11 wherein z is 2 or more.

23. The process of claim 1 wherein the process is a continuous process.

24. The process of claim 1 wherein the olefins are aliphatic or alicyclic hydrocarbons.

25. The process of claim 1 wherein the olefins are linear or branched alpha-olefins.

26. The process of claim 1 wherein the olefins are C2 to C40 linear or branched alpha-olefins

27. The process of claim 1 wherein the olefins are selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene.

28. The process of claim 1 wherein the fluorocarbon consists essentially of hydrofluorocarbons.

29. The process of claim 1 where the polymer produced has a crystallinity of less than 20%.

2. A solution process to produce polyolefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorinated hydrocarbon at a polymerization temperature above the melting point of the wet polymer, wherein the fluorinated hydrocarbon is present at 5 volume % or more, based upon the total volume of fluorocarbons and any hydrocarbon solvents present.

30. The process of claim 2 wherein the polymerization temperature is above 100°

C.

31. The process of claim 2 wherein the polymerization temperature is above 120°

C.

32. The process of claim 2 wherein the polymerization temperature is between 100 and 250°

C.

33. The process of claim 2 wherein the polymerization effluent comprises a hydrocarbon solvent or diluent.

34. The process of claim 33 wherein the hydrocarbon solvent or diluent is selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, octane, isooctane, and cyclohexane.

35. The process of claim 2 where the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the volume of the polymerization medium.

36. The process of claim 2 wherein the fluorinated hydrocarbon comprises a perfluorinated hydrocarbon.

37. The process of claim 2 wherein the fluorinated hydrocarbon comprises a hydrofluorocarbon.

38. The process of claim 2 wherein the fluorinated hydrocarbon is represented by the formula:

C_xH_yF_z wherein x is an integer from 1 to 40, y is an integer greater than or equal to 0 and z is an integer and is at least one.

39. The process of claim 2 wherein the fluorinated hydrocarbon is selected from the group consisting of fluoromethane;

difluoromethane;

trifluoromethane;

fluoroethane;

1,1-difluoroethane;

1,2-difluoroethane;

1,1,1-trifluoroethane;

1,1,2-trifluoroethane;

1,1,1,2-tetrafluoroethane;

1,1,2,2-tetrafluoroethane;

1,1,1,2,2-pentafluoroethane;

1-fluoropropane;

2-fluoropropane;

1,1-difluoropropane;

1,2-difluoropropane;

1,3-difluoropropane;

2,2-difluoropropane;

1,1,1-trifluoropropane;

1,1,2-trifluoropropane;

1,1,3-trifluoropropane;

1,2,2-trifluoropropane;

1,2,3-trifluoropropane;

1,1,1,2-tetrafluoropropane;

1,1,1,3-tetrafluoropropane;

1,1,2,2-tetrafluoropropane;

1,1,2,3-tetrafluoropropane;

1,1,3,3-tetrafluoropropane;

1,2,2,3-tetrafluoropropane;

1,1,1,2,2-pentafluoropropane;

1,1,1,2,3-pentafluoropropane;

1,1,1,3,3-pentafluoropropane;

1,1,2,2,3-pentafluoropropane;

1,1,2,3,3-pentafluoropropane;

1,1,1,2,2,3-hexafluoropropane;

1,1,1,2,3,3-hexafluoropropane;

1,1,1,3,3,3-hexafluoropropane;

1,1,1,2,2,3,3-heptafluoropropane;

1,1,1,2,3,3,3-heptafluoropropane;

1-fluorobutane;

2-fluorobutane;

1,1-difluorobutane;

1,2-difluorobutane;

1,3-difluorobutane;

1,4-difluorobutane;

2,2-difluorobutane;

2,3-difluorobutane;

1,1,1-trifluorobutane;

1,1,2-trifluorobutane;

1,1,3-trifluorobutane;

1,1,4-trifluorobutane;

1,2,2-trifluorobutane;

1,2,3-trifluorobutane;

1,3,3-trifluorobutane;

2,2,3-trifluorobutane;

1,1,1,2-tetrafluorobutane;

1,1,1,3-tetrafluorobutane;

1,1,1,4-tetrafluorobutane;

1,1,2,2-tetrafluorobutane;

1,1,2,3-tetrafluorobutane;

1,1,2,4-tetrafluorobutane;

1,1,3,3-tetrafluorobutane;

1,1,3,4-tetrafluorobutane;

1,1,4,4-tetrafluorobutane;

1,2,2,3-tetrafluorobutane;

1,2,2,4-tetrafluorobutane;

1,2,3,3-tetrafluorobutane;

1,2,3,4-tetrafluorobutane;

2,2,3,3-tetrafluorobutane;

1,1,1,2,2-pentafluorobutane;

1,1,1,2,3-pentafluorobutane;

1,1,1,2,4-pentafluorobutane;

1,1,1,3,3-pentafluorobutane;

1,1,1,3,4-pentafluorobutane;

1,1,1,4,4-pentafluorobutane;

1,1,2,2,3-pentafluorobutane;

1,1,2,2,4-pentafluorobutane;

1,1,2,3,3-pentafluorobutane;

1,1,2,4,4-pentafluorobutane;

1,1,3,3,4-pentafluorobutane;

1,2,2,3,3-pentafluorobutane;

1,2,2,3,4-pentafluorobutane;

1,1,1,2,2,3-hexafluorobutane;

1,1,1,2,2,4-hexafluorobutane;

1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;

1,1,1,2,4,4-hexafluorobutane;

1,1,1,3,3,4-hexafluorobutane;

1,1,1,3,4,4-hexafluorobutane;

1,1,1,4,4,4-hexafluorobutane;

1,1,2,2,3,3-hexafluorobutane;

1,1,2,2,3,4-hexafluorobutane;

1,1,2,2,4,4-hexafluorobutane;

1,1,2,3,3,4-hexafluorobutane;

1,1,2,3,4,4-hexafluorobutane;

1,2,2,3,3,4-hexafluorobutane;

1,1,1,2,2,3,3-heptafluorobutane;

1,1,1,2,2,4,4-heptafluorobutane;

1,1,1,2,2,3,4-heptafluorobutane;

1,1,1,2,3,3,4-heptafluorobutane;

1,1,1,2,3,4,4-heptafluorobutane;

1,1,1,2,4,4,4-heptafluorobutane;

1,1,1,3,3,4,4-heptafluorobutane;

1,1,1,2,2,3,3,4-octafluorobutane;

1,1,1,2,2,3,4,4-octafluorobutane;

1,1,1,2,3,3,4,4-octafluorobutane;

1,1,1,2,2,4,4,4-octafluorobutane;

1,1,1,2,3,4,4,4-octafluorobutane;

1,1,1,2,2,3,3,4,4-nonafluorobutane;

1,1,1,2,2,3,4,4,4-nonafluorobutane;

1-fluoro-2-methylpropane;

1,1-difluoro-2-methylpropane;

1,3-difluoro-2-methylpropane;

1,1,1-trifluoro-2-methylpropane;

1,1,3-trifluoro-2-methylpropane;

1,3-difluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-methylpropane;

1,1,3-trifluoro-2-(fluoromethyl)propane;

1,1,1,3,3-pentafluoro-2-methylpropane;

1,1,3,3-tetrafluoro-2-(fluoromethyl)propane;

1,1,1,3-tetrafluoro-2-(fluoromethyl)propane;

fluorocyclobutane;

1,1-difluorocyclobutane;

1,2-difluorocyclobutane;

1,3-difluorocyclobutane;

1,1,2-trifluorocyclobutane;

1,1,3-trifluorocyclobutane;

1,2,3-trifluorocyclobutane;

1,1,2,2-tetrafluorocyclobutane;

1,1,3,3-tetrafluorocyclobutane;

1,1,2,2,3-pentafluorocyclobutane;

1,1,2,3,3-pentafluorocyclobutane;

1,1,2,2,3,3-hexafluorocyclobutane;

1,1,2,2,3,4-hexafluorocyclobutane;

1,1,2,3,3,4-hexafluorocyclobutane; and

1,1,2,2,3,3,4-heptafluorocyclobutane.

40. The process of claim 2 wherein the fluorinated hydrocarbon is selected from the group consisting of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane, and 1,1,1,2-tetrafluoroethane.

41. The process of claim 2 wherein the fluorinated hydrocarbon is selected from the group consisting of 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, octafluorocyclobutane, and 2,3-dihydrodecafluoropentane.

42. The process of claim 2 wherein the polymerization medium comprises ethylene.

43. The process of claim 2 where the polymerization medium comprises propylene.

44. The process of claim 2 where the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.

45. The process of claim 2 wherein the polymerization further comprises a hydrocarbon and the fluorinated hydrocarbon is soluble in the hydrocarbon.

46. The process of claim 2 where the fluorinated hydrocarbon is present at 20 to 90 volume %, based upon the volume of the polymerization medium.

47. The process of claim 2 wherein the fluorinated hydrocarbon is present at least 1 weight % based upon the weight of the fluorinated hydrocarbon and any hydrocarbon solvent or diluent present, and where the process further comprises recovering a polymer having an Mw of 70,000 or more and a percent crystallinity of 20% or more.

48. The process of claim 2 further comprising introducing a fluorinated hydrocarbon into the polymer effluent.

49. The process of claim 38 wherein z is 2 or more.

50. The process of claim 2 wherein the process is a continuous process.

51. The process of claim 2 wherein the olefins are aliphatic or alicyclic hydrocarbons.

52. The process of claim 2 wherein the olefins are linear or branched alpha-olefins.

53. The process of claim 2 wherein the olefins are C2 to C40 linear or branched alpha-olefins

54. The process of claim 2 wherein the olefins are selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene.

55. The process of claim 2 wherein the fluorocarbon consists essentially of hydrofluorocarbons.

56. The process of claim 2 where the polymer produced has a crystallinity of less than 20%.