Polymerization Process

• US 20080033127A1
• Filed: 06/20/2005
• Published: 02/07/2008
• Est. Priority Date: 06/20/2005
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Shirodkar, Pradeep, Speed, Charles, Shutt, John, Hagerty, Robert, Jiang, Peijun
• Granted Patent: US 7,799,882 B2
• Time in Patent Office: Days
• US Class Current: 526/206
• 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 10/06 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 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

This invention relates to a multiple phase polymerization process to produce polyolefins comprising contacting olefins and a homogeneous catalyst or catalyst system at a temperature between the melting point of the dry polymer and 80° C. below the melting point of the dry polymer in the presence of a fluorinated hydrocarbon. This invention also relates to a process to produce polyethylene comprising contacting a homogeneous catalyst or catalyst system with ethylene and from 0 to 40 weight % of one or more C3 to C40 olefin comonomer(s) in the presence of a fluorinated hydrocarbon and optionally a hydrocarbon solvent at a temperature below the reaction medium melting point. This invention also relates to a process to produce polypropylene comprising contacting a homogeneous catalyst or catalyst system with propylene and from 0 to 50 weight % of one or more of ethylene and C4 to C40 olefin comonomer(s) in the presence of a fluorinated hydrocarbon and optionally a hydrocarbon solvent at a temperature below the reaction medium melting point.

Claims

1. (canceled)

2. (canceled)

3. A process to produce polypropylene comprising contacting a homogeneous catalyst or catalyst system with propylene and from 0 to 50 weight % of one or more of ethylene and C4 to C40 olefin comonomer(s), based upon the weight of total monomers present, in the presence of a fluorinated hydrocarbon, and optionally a hydrocarbon solvent or diluent at a temperature below the reaction medium melting point and above 50°

C.

7. The process of claim 3 wherein the polymerization temperature is 70°

C. or more.

8. The process of claim 3 wherein the polymerization temperature is 80°

C. or more.

9. The process of claim 3 wherein the polymerization medium further comprises a hydrocarbon solvent or diluent.

10. The process of claim 9 wherein the hydrocarbon solvent or diluent is selected from the group consisting of propane, n-butane, isobutane, mixed butanes, n-pentane, cyclo-pentane, isopentane, neopentane, n-hexane, isohexane, mixed hexanes, cyclohexane, octane and desulphurized light virgin naphtha.

11. The process of claim 3 where the fluorinated hydrocarbon is present at 20 to 99 volume %, based upon the volume of the polymerization medium.

15. The process of claim 3 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.

16. The process of claim 3 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.

17. The process of claim 3 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.

19. The process of claim 3 wherein the polymerization medium comprises ethylene.

20. The process of claim 3 where the polymerization medium comprises propylene.

21. The process of claim 3 where the fluorocarbon is not a perfluorinated C4 to C10 alkane.

23. The process of claim 3 wherein the process is a continuous process.

24. The process of claim 3 wherein the olefins are aliphatic or alicyclic hydrocarbons.

26. The process of claim 3 wherein the olefins are C2 to C40 linear or branched alpha-olefins

27. The process of claim 3 wherein the olefins are selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene.

28. The process of claim 27 wherein the fluorocarbon consists essentially of hydrofluorocarbons.

29. The process of claim 15 wherein z is 2 or more.

4. A slurry process to polymerize olefins comprising contacting olefins and a homogeneous catalyst system in the presence of a fluorinated hydrocarbon at a temperature of 70°

C. or more.

5. The process of claim 4 wherein the temperature is above 70°

C. and below the melting point of the dry polymer.

6. The process of claim 4 wherein the olefin polymer produced has at least 3% crystallinity.

12. The process of claim 4 where the fluorinated hydrocarbon is present at 20 to 70 volume %, based upon the volume of the polymerization medium.

13. The process of claim 30 wherein the fluorinated hydrocarbon comprises a perfluorinated hydrocarbon.

14. The process of claim 4 wherein the fluorinated hydrocarbon comprises a hydrofluorocarbon.

18. The process of claim 4 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.

25. The process of claim 4 wherein the olefins are linear or branched alpha-olefins.

30. The process of claim 4 wherein the polymerization temperature is 80°

C. or more.

31. The process of claim 4 wherein the polymerization medium further comprises a hydrocarbon solvent or diluent.

32. The process of claim 4 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.

33. The process of claim 4 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.

34. The process of claim 4 wherein the polymerization medium comprises ethylene.

35. The process of claim 4 where the polymerization medium comprises propylene.

36. The process of claim 4 where the fluorocarbon is not a perfluorinated C4 to C10 alkane.

37. The process of claim 4 wherein the process is a continuous process.

38. The process of claim 4 wherein the olefins are selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene.

39. The process of claim 32 where z is 2 or more.

22. A multiple phase polymerization process to produce polyolefins comprising contacting olefins and a homogeneous catalyst or catalyst system at a temperature between the melting point of the dry polymer and 25°

C. below the melting point of the dry polymer in the presence of a fluorocarbon provided that the temperature is above 70°

C.

40. A process to produce polyolefins comprising contacting olefins and a homogeneous catalyst or catalyst system in the presence of a fluorinated hydrocarbon at a temperature below the melting point of the dry polymer and above 70°

C., where the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the total volume of the mixture of fluorinated hydrocarbon, any hydrocarbon solvent or diluent present and any unreacted monomers present, wherein the olefins are selected from the group consisting of C2 to C40 olefins.

41. A process to produce polyethylene comprising contacting a homogeneous catalyst or catalyst system with ethylene and from 0 to 40 weight % of one or more C3 to C40 olefin comonomer(s), based upon the weight of total monomers present, in the presence of a fluorinated hydrocarbon, and optionally a hydrocarbon solvent or diluent at a temperature below the reaction medium melting point and above 50°

C., where the fluorinated hydrocarbon is present at more than 5 weight %, based upon the weight of the fluorinated hydrocarbon and any hydrocarbon solvent or diluent present.