Impact copolymers

• US 7,662,892 B2
• Filed: 06/20/2005
• Issued: 02/16/2010
• Est. Priority Date: 06/21/2004
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Iaccino, Larry L., Jiang, Peijun, Shutt, John Richard, Shirodkar, Pradeep P., Hagerty, Robert Olds, Speed, Charles Stanley
• Primary Examiner(s): Teskin; Fred M
• Application Number:
  US11/628,183
• Publication Number:
  US 20070225455A1
• Time in Patent Office: 1,702 Days
• Field of Search: 525/53, 526/65, 526/206
• US Class Current: 526/65
• 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 110/02 Ethene
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 2/01 characterised by special features of the polymerisation apparatus used
• 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 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/654 with magnesium or compounds thereof
• 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 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

This invention relates to a continuous process to prepare olefin impact copolymers comprising producing a semi-crystalline olefin polymer in a first reactor and then transferring the reactor contents to a second reactor where a low crystallinity olefin polymer is produced in the presence of the semi-crystalline polymer, where a fluorinated hydrocarbon is present in the polymerization medium of the first reactor, the second reactor or both reactors.

Claims

1. A continuous process to prepare olefin impact copolymers having a melting point of at least 145°

C. comprising producing a semi-crystalline olefin polymer in a first reactor and then transferring the reactor contents to a second reactor to produce a low crystallinity olefin polymer in the presence of the semi-crystalline polymer, wherein a fluorinated hydrocarbon is present in a polymerization medium of the first reactor, the second reactor or both reactors.

2. The process as claimed in claim 1, comprising contacting one or more olefins and a catalyst system in a first reactor optionally in the presence of a fluorinated hydrocarbon and thereafter transferring the reactor contents to the second reactor and introducing one or more additional olefin monomers, in the presence of a fluorinated hydrocarbon, and thereafter obtaining an impact copolymer.

3. The process of claim 1 wherein ethylene is polymerized in the first or second reactor.

4. The process of claim 1 wherein propylene is polymerized in the first or second reactor.

5. The process as claimed in claim 4 wherein the olefin in the first reactor is or includes propylene, and the additional olefin monomers in the second reactor comprises ethylene, propylene, or both.

6. The process as claimed in claim 4 comprising contacting propylene and a catalyst system in the first reactor in the presence of a fluorinated hydrocarbon and thereafter transferring the reactor contents to the second reactor and introducing ethylene and, optionally propylene, optionally in the presence of a fluorinated hydrocarbon, and thereafter obtaining an impact copolymer.

7. The process of claim 1, wherein the polymerization medium of either or both reactors also comprises a hydrocarbon solvent or diluent.

8. The process of claim 7 wherein the hydrocarbon solvent or diluent comprises one or more of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, and cyclohexane.

9. The process of claim 1, wherein the fluorinated hydrocarbon is present in an amount of from 0.1 to 99 volume %, based upon the volume of the polymerization medium in the reactor.

10. The process of claim 9, wherein the fluorinated hydrocarbon is present in an amount of from 5 to 90 volume %, based upon the volume of the polymerization medium in the reactor.

11. The process of claim 1, wherein the fluorinated hydrocarbon is present in an amount of more than 5 weight %, based upon the combined weight of the fluorinated hydrocarbon and any hydrocarbon solvent present in the reactor.

12. The process of claim 1 wherein the fluorinated hydrocarbon comprises a compound 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.

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

14. The process of claim 1, wherein the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.

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

16. The process of claim 1 wherein the fluorinated hydrocarbon comprises one or more 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 1 wherein the fluorinated hydrocarbon comprises one or more of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane, and 1,1,1,2-tetrafluoroethane.

18. The process of claim 1 wherein the fluorinated hydrocarbon comprises one or more 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.

20. The process of claim 1 wherein the first or second reactor is a slurry phase reactor.

22. The process of claim 1 wherein the reactors operate in the same phase.

19. A continuous process to prepare olefin impact copolymers comprising producing a semi-crystalline olefin polymer in a first reactor and then transferring the reactor contents to a second reactor to produce a low crystallinity olefin polymer in the presence of the semi-crystalline polymer, wherein a fluorinated hydrocarbon is present in a polymerization medium of the first reactor, the second reactor or both reactors, wherein the first or second reactor is a gas phase reactor.

21. A continuous process to prepare olefin impact copolymers comprising producing a semi-crystalline olefin polymer in a first reactor and then transferring the reactor contents to a second reactor to produce a low crystallinity olefin polymer in the presence of the semi-crystalline polymer, wherein a fluorinated hydrocarbon is present in a polymerization medium of the first reactor, the second reactor or both reactors, wherein the first or second reactor is a solution phase reactor.

23. A continuous process to prepare olefin impact copolymers comprising producing a semi-crystalline olefin polymer in a first reactor and then transferring the reactor contents to a second reactor to produce a low crystallinity olefin polymer in the presence of the semi-crystalline polymer, wherein a fluorinated hydrocarbon is present in a polymerization medium of the first reactor, the second reactor or both reactors, wherein the reactors operate in different phases.

24. A continuous process to prepare impact copolymers having a melting point of at least 145°

C. comprising producing a semi-crystalline polymer in a first reaction zone and then transferring the semi-crystalline polymer to a second reaction zone to produce a low crystallinity polymer in the presence of the semi-crystalline polymer, wherein a fluorinated hydrocarbon is present in a polymerization medium of the first reaction zone, the second reaction zone or both reaction zones.

25. The process of claim 24 wherein the fluorocarbon is present in the first reaction zone.

26. The process of claim 24 wherein the fluorocarbon is present in the second reaction zone.

27. The process as claimed in claim 24 comprising contacting one or more olefins and the catalyst system in a first reaction zone optionally in the presence of a fluorinated hydrocarbon and thereafter transferring the reaction zone contents to the second reaction zone and introducing one or more additional olefin monomers, in the presence of a fluorinated hydrocarbon, and thereafter obtaining an impact copolymer.

28. The process of claim 24 wherein ethylene is polymerized in the first or second reaction zone.

29. The process of claim 24 wherein propylene is polymerized in the first or second reaction zone.

30. The process as claimed in claim 29 to produce impact polypropylene copolymers, wherein the olefin in the first reaction zone is or includes propylene, and the additional olefin monomers in the second reaction zone comprises ethylene and, optionally propylene.

31. The process as claimed in claim 29 to produce impact polypropylene copolymers, comprising contacting propylene and a catalyst system in the first reaction zone in the presence of a fluorinated hydrocarbon and thereafter transferring the reaction zone contents to the second reaction zone and introducing ethylene and, optionally propylene, optionally in the presence of a fluorinated hydrocarbon, and thereafter obtaining the impact copolymer.

32. The process of claim 24, wherein the polymerization medium of either or both reaction zones also comprises a hydrocarbon solvent or diluent.

33. The process of claim 32 wherein the hydrocarbon solvent or diluent comprises one or more of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, and cyclohexane.

34. The process of claim 24, wherein when the fluorinated hydrocarbon is present in the polymerization medium of the first reaction zone, the second reaction zone or both reaction zones, the fluorinated hydrocarbon is present in an amount of from 0.1 to 99 volume %, based upon the volume of the polymerization medium in the reaction zone, where the fluorinated hydrocarbon is present.

35. The process of claim 34, where the fluorinated hydrocarbon is present in an amount of from 5 to 90 volume %, based upon the volume of the polymerization medium in the reaction zone, where the fluorinated hydrocarbon is present.

36. The process of claim 24, wherein the polymerization medium of either or both reaction zones also comprises a hydrocarbon solvent or diluent wherein the fluorinated hydrocarbon present in either or both reaction zones is present in an amount of more than 5 weight %, based upon the combined weight of the fluorinated hydrocarbon and any hydrocarbon solvent present in the reaction zone.

37. The process of claim 24 wherein the fluorinated hydrocarbon comprises a compound 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.

38. The process of claim 37, wherein the fluorinated hydrocarbon comprises a perfluorinated hydrocarbon.

39. The process of claim 38, where the perfluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.

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

41. The process of claim 37 wherein the fluorinated hydrocarbon comprises one or more 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.

42. The process of claim 41 wherein the fluorinated hydrocarbon comprises one or more 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.

43. The process of claim 24 wherein the first reaction zone and the second reaction zone are present in the same reactor.

44. The process of claim 40 wherein the fluorinated hydrocarbon comprises one or more of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane, and 1,1,1,2-tetrafluoroethane.