Polymerization Process

• US 20070244279A1
• Filed: 06/20/2005
• Published: 10/18/2007
• 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, Stavens, Kevin, Laird, Randall, Speed, Charles, Shutt, John, Hagerty, Robert
• Granted Patent: US 7,414,100 B2
• Time in Patent Office: Days
• US Class Current: 526/206
• CPC Class Codes: C08F 2/002 Scale prevention in a polymerisation reactor or its auxiliary parts
• CPC Class Codes: C08F 2/06 Organic solvent
• 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 2500/20 Activation energy or enthalpy

Abstract

This invention relates to a process to increase the amount of polymer solute in a polymerization medium or effluent comprising introducing a fluorocarbon into the polymerization medium or effluent in an amount effective to increase the amount of polymer solute in the polymerization medium or effluent by at least 3% without causing precipitation of polymer solute from the polymerization medium or effluent, as compared to the same polymerization medium or effluent without the fluorocarbon present. This invention also relates to a process to reduce the viscosity of a polymerization medium or effluent comprising introducing a fluorocarbon into the polymerization medium or effluent in an amount effective to reduce the viscosity of the polymerization medium or effluent by at least 3% without causing precipitation of polymer solute from the polymerization medium or effluent, as compared to the same polymerization medium or effluent without the fluorocarbon present.

Claims

1. A solution olefin polymerization process, in which the olefin polymer is present as a solute in a polymerization medium, comprising introducing a fluorinated hydrocarbon into the polymerization medium in an amount effective to increase the amount of polymer solute in the polymerization medium by at least 3%, as compared to the same polymerization medium without the fluorinated hydrocarbon present, without causing precipitation of polymer solute from the polymerization medium, where the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.

4. The process of claim 1 wherein the polymerization medium comprises a hydrocarbon.

5. The process of claim 4 wherein the hydrocarbon comprises one or more of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, and cyclohexane.

6. The process of claim 1 where the fluorinated hydrocarbon is present at 0.1 to 20 volume %, based upon the volume of the polymerization medium or polymerization effluent.

7. 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.

8. The process of claim 1 wherein the fluorinated hydrocarbon comprises 1,1,1,3,3,3-hexafluoropropane.

9. The process of claim 1 where the fluorinated hydrocarbon comprises 1,1,1,2-tetrafluoroethane.

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

11. 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.

12. The process or use 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.

13. The process or use 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.

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

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

16. The process of claim 1, where the fluorinated hydrocarbon comprises octafluorocyclobutane.

17. The process of claim 1 where the fluorinated hydrocarbon is present at more than 5 weight %, based upon the weight of the fluorocarbon and any hydrocarbon solvent present in the reactor.

2. (canceled)

3. A process for reducing the viscosity of an olefin polymerization effluent comprising introducing a fluorinated hydrocarbon into the polymerization effluent in an amount effective to reduce the viscosity of the polymerization effluent by at least 3% as compared to the same polymerization medium without the fluorinated hydrocarbon present, without causing precipitation of polymer solute from the polymerization effluent, where the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.

18. The process of claim 3 wherein the effluent is divided into streams including a waste stream and the waste stream is passed through activated carbon prior to being sent to a flare.

19. The process of claim 3 wherein the polymerization medium comprises a hydrocarbon and the hydrocarbon comprises one or more of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, and cyclohexane.

20. The process of claim 3 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-tetrafluorobutahe;

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.

21. The process of claim 3 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.

22. The process of claim 3 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.

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

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

25. The process of claim 3 where the fluorinated hydrocarbon is present at more than 5 weight %, based upon the weight of the fluorocarbon and any hydrocarbon solvent present in the reactor.

26. The process of claim 3 wherein the polymerization medium comprises a hydrocarbon.