Jiang, Peijun (League City, TX, US)
Shutt, John Richard (Merchtem, BE)
Speed, Charles Stanley (Dayton, TX, US)
Laird, Randall B. (Pasadena, TX, US)
Stavens, Kevin Bruce (Seabrook, TX, US)
Hagerty, Robert Olds (La Porte, TX, US)

Plaque It!

11/628166

08/19/2008

06/20/2005

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ExxonMobil Chemical Patents Inc. (Houston, TX, US)

526/206

526/74, 528/482, 528/491

C08F2/06; C08F6/06; C08F10/02

526/206, 526/74, 528/482, 528/491

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Teskin, Fred M.

Bell, Catherine L.

This application is the national phase entry into the United States Patent Office of international application number PCT/US2005/021644 filed Jun. 20, 2005, which claims benefit of and priority to U.S. Provisional Patent Application Ser. No. 60/581,522 filed Jun. 21, 2004.

The invention claimed is:

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, where the olefin polymer is at least 75 mole % hydrocarbon monomer and the monomers to be polymerized are not fluoromonomers.

2. 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, wherein the polymer solute is a polymer of C2 to C40 linear or branched alpha-olefins.

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

4. 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, and wherein the polymerization medium comprises a hydrocarbon comprising one or more of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, and cyclohexane.

5. 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.

6. 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.

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

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

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

10. A solution olefin polymerization process, in which the olefin polymer: 1) comprises 100 mole % hydrocarbon monomer, and 2) 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, 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.

11. 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.

12. 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.

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

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

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

16. 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.

17. 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, 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.

18. 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, 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.

19. A process for reducing the viscosity of an olefin polymerization effluent comprising olefin polymer comprising at least 100 mole % hydrocarbon monomer selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof, said process 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, 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.

20. The process of claim 2 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.

21. The process of claim 2 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.

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

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

24. The process of claim 2 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.

25. The process of claim 2 wherein the polymerization medium comprises a hydrocarbon.

FIELD OF THE INVENTION

This invention relates to the use of a fluorocarbon in a polymerization process to reduce the viscosity of the polymerization medium or effluent and or to increase the amount of solute in the polymerization medium or effluent.

BACKGROUND OF THE INVENTION

Unsaturated monomers, particularly olefin monomers, are polymerized in a variety of polymerization processes using a wide variety of catalysts and catalyst systems. One of the most common polymerization processes used in the production of olefin based polymers such as polyethylene, polypropylene, polybutene, etc, is a solution based process. In such a process the formed polymer is dissolved in the polymerization medium. Often, the catalyst and monomer are also dissolved in the polymerization medium, but that is not a requirement of a “solution” process. In typical solution processes, the polymerization temperature may be at, above or below the melting point of the dry polymer. For example, in typical solution phase polyethylene processes, polymerization takes place in a hydrocarbon solvent at temperatures above the melting point of the polymer and the polymer is typically recovered by vaporization of the solvent and any unreacted monomer. In some cases solvents are used while in others, the monomer to be polymerized also acts as the solvent (e.g. a bulk process).

In each of these processes, there remain factors that influence not only the rate and volume at which the polymerization can run, but can also influence the properties of polymer produced. In a typical solution process, the polymer formed is dissolved in the solvent. The higher the concentration of the polymer in the solvent, the higher the viscosity of the polymerization reaction mixture (also called polymerization medium or medium) containing polymer, monomers and solvent. High viscosity in the polymerization reactor associated with solution process is often a limiting step for process efficiency and polymer production. High viscosity can lead to difficulties in efficient mixing in the reactor, difficulties in maintaining a homogeneous system, difficulties in avoiding product property drift (heterogeneity), and, process control problems. This is especially true for polymerization processes where the polymers produced are to have a molecular weight higher than the entanglement molecular weight. Higher operating temperature may help address these problems by reducing the viscosity of the polymerization medium, however the molecular weight of the polymer product tends to decrease with reaction temperature. Thus production of higher molecular weight polymers in solution processes is limited by the viscosity of the polymerization medium. This problem exists even with the advent of new catalyst systems. Metallocene catalysts (e.g. group 4-7 transition metal compounds having at least one cyclopentadienyl group attached to the metal) allow polymerizations to be performed at a high temperatures, such that a higher polymer concentration of higher molecular weight copolymers (e.g., 16-18 wt % for ethylene-propylene-diene monomer copolymers) can be achieved in the reactor effluent without significant operation difficulties as compared to a conventional solution process (e.g., 7-13 wt % at 30-50° C. for ethylene-propylene-diene monomer copolymers). Similarly, high reaction temperatures tend to improve the polymerization rate and solvent recovery in a solution process, however, the polymer concentration still tends to be much lower than that in an equivalent slurry process. Further, it is also difficult to produce high molecular weight polymers (>100 Mooney) in a solution process due to the nature of high viscosity of a polymer having a Mooney viscosity of 100 or more. Thus there is a need in the art for a means to reduce the viscosity and/or increase the polymer concentration in a solution polymerization process, among other things.

Likewise, viscosity and other characteristics of a polymer solution are also important factors in determining process parameters, such as throughput, volume, temperature and the like. In some systems, it is possible to have a higher amount of polymer solute present, however the viscosity of that solution makes it difficult to handle,—i.e. the more viscous the solution, the more difficult it is to pump and the more likely it is to foul. Thus the process may also be limited by solution viscosity and there is a need in the art for means to reduce solution viscosity while maintaining or even increasing solute concentration.

U.S. Pat. No. 3,470,143 discloses a process to produce a boiling-xylene soluble polymer in a slurry using certain fluorinated organic carbon compounds.

U.S. Pat. No. 5,990,251 discloses a gas phase process using a Ziegler-Natta catalyst system modified with a halogenated hydrocarbon, such as chloroform.

EP 0 459 320 A discloses polymerization in polar aprotic solvents, such as halogenated hydrocarbons.

U.S. Pat. No. 5,780,565 discloses dispersion polymerizations of polar monomers under super-atmospheric conditions such that the fluid is a liquid or supercritical fluid, the fluid being carbon dioxide, a hydrofluorocarbon, a perfluorocarbon or a mixture thereof.

U.S. Pat. No. 5,624,878 discloses the polymerization using “constrained geometry metal complexes” of titanium and zirconium.

U.S. Pat. No. 2,534,698, U.S. Pat. No. 2,644,809 and U.S. Pat. No. 2,548,415 disclose preparation of butyl rubber type elastomers in fluorinated solvents.

U.S. Pat. No. 6,534,613 discloses use of hydrofluorocarbons as catalyst modifiers.

U.S. Pat. No. 4,950,724 disclose the polymerization of vinyl aromatic monomers in suspension polymerization using fluorinated aliphatic organic compounds.

WO 02/34794 discloses free radical polymerizations in certain hydrofluorocarbons.

WO 02/04120 discloses a fluorous bi-phasic systems.

WO 02/059161 discloses polymerization of isobutylene using fluorinated co-initiators.

EP 1 323 746 shows loading of biscyclopentadienyl catalyst onto a silica support in perfluorooctane and thereafter the prepolymerization of ethylene at room temperature.

U.S. Pat. No. 3,056,771 discloses polymerization of ethylene using TiCl ₄ /(Et) ₃ Al in a mixture of heptane and perfluoromethylcyclohexane, presumably at room temperature, further a mixture of 30% perfluoromethylcyclohexane in heptane was used to cause the polymer in the slurry to float.

Additional references of interest include:

Designing Solvent Solutions, Chemical and Engineering News, Oct. 13, 2003 (www.CEN-online.org); Polymer Synthesis Using Hydrofluorocarbon Solvents, Wood, Colin, et al. Macromolecules, Vol. 35, Number 18, pages 6743-6746, 2002; Perfluorinated Polyethers for the Inmobilisation of Homogeneous Nickel Catalysts, Keim, W. et al., Journal of Molecular Catalysis A: Chemical 139 (1999) 171-175; RU2195465; US20020086908 A1; WO200251875 A1; US2002/0032291 A1; U.S. Pat. Nos. 3,397,166; 3,440,219; 6,111,062; 5,789,504; 5,703,194; 5,663,251; 5,608,002; 5,494,984; 5,310,870; 5,182,342; 2,603,626; 2,494,585; 2,474,571; WO 02/051875 A1; U.S. Pat. Nos. 6,133,389; 6,096,840; 6,107,423; 6,037,483; 5,981,673; 5,939,502; 5,939,501; 5,674,957; 5,872,198; 5,959,050; 5,821,311; 5,807,977; 5,688,838; 5,668,251; 5,668,250; 5,665,838; 5,663,255; 5,552,500; 5,478,905; 5,459,212; 5,281,680; 5,135,998; 5,105,047; 5,032,656; 4,166,165; 4,123,602; 4,100,225; 4,042,634; US 2002/0132910 A1; US 2002/0151664 A1; US 2002/0183457 A1; US 2002/0183471 A1; US 2003/0023013 A1; US 2001/0012880 A1; US 2001/0018144 A1; US 2002/0002219 A1; US 2002/0028884 A1; US 2002/0052454 A1; US 2002/0055580 A1; US 2002/0055581; US 2002/0055599 A1, US 2002/0065383; US 2002/0086908 A1; US 2002/0128411 A1; U.S. Pat. Nos. 3,269,972, 3,331,822; US

SUMMARY OF THE INVENTION

This invention relates to 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.

This invention relates to a process to increase the amount of olefin polymer solute in a polymerization medium or effluent comprising introducing a fluorocarbon into the olefin 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.

This invention also relates to a process to increase the polymer solute present in a polymerization medium or effluent and reduce the viscosity of 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 present by at least 1%, and 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.

This invention also relates to a solution polymerization process for producing a polyolefins, in which the polyolefin forms 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.

Definitions

For purposes of this invention and the claims thereto, the term copolymers means any polymer comprising two or more monomers.

For the purposes of this invention and the claims thereto when a polymer is referred to as comprising a monomer, the olefin present in the polymer is the polymerized form of the monomer. Likewise when catalyst components are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the active form of the component is the form that reacts with the monomers to produce polymers. In addition, a reactor is any container(s) in which a chemical reaction occurs.

As used herein, the new notation numbering scheme for the Periodic Table Groups are used as set out in C HEMICAL AND E NGINEERING N EWS , 63 (5), 27 (1985).

As used herein, Me is methyl, t-Bu and ^t Bu are tertiary butyl, iPr and ⁱ Pr are isopropyl, Cy is cyclohexyl, and Ph is phenyl.

For purposes of this disclosure, the term oligomer refers to compositions having 2-75 mer units and the term polymer refers to compositions having 76 or more mer units. A mer is defined as a unit of an oligomer or polymer that originally corresponded to the monomer(s) used in the oligomerization or polymerization reaction. For example, the mer of polyethylene would be ethylene.

The term “catalyst system” is defined to mean a catalyst precursor/activator pair. When “catalyst system” is used to describe such a pair before activation, it means the unactivated catalyst (precatalyst) together with an activator and, optionally, a co-activator. When it is used to describe such a pair after activation, it means the activated catalyst and the activator or other charge-balancing moiety.

The transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system.

Catalyst precursor is also often referred to as precatalyst, catalyst, catalyst compound, catalyst precursor, transition metal compound or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably.

DETAILED DESCRIPTION

This invention relates in part to a solution process for polymerization using fluorinated hydrocarbon(s) or a mixture of fluorinated hydrocarbons and hydrocarbon solvents to provide a means of increasing polymer solute concentration and/or reducing viscosity of polymerization medium without polymer precipitation. Without wishing to be bound by any theory, we believe that one can select one or more fluorocarbons to add in controlled amounts to the hydrocarbon polymer solution such that the medium remains single phase, e.g. homogeneous, and or that the interaction effect between the fluorinated hydrocarbon and the dissolved polymer somehow contributes to causing the polymer chain to have a smaller coil dimension partially thereby decreasing the potential polymer-polymer entanglements and thus decreasing the solution viscosity.

This invention further relates to a modified polymerization process, where the polymer is in solution in the polymerization medium or effluent and the viscosity of the polymerization effluent exiting the reactor is modified by the addition of a fluorocarbon and or the amount of polymer solute in the solvent medium or effluent is increased (as compared to the same system without the fluorocarbon). Preferably, the fluorocarbon is added in an amount such that the polymer remains in solution and does not precipitate. Preferably the fluorocarbon has the effect of increasing the amount of polymer solute present in the polymerization medium and/or effluent and or reducing the viscosity of the polymerization medium and/or effluent (as compared to the same system without the fluorocarbon). The fluorocarbon may be added before, during or after the polymerization. Likewise the fluorocarbon may be added at the reactor exit or during recovery processes after the polymer has exited the reactor. Likewise the fluorocarbon may be added to the reactor as part of the monomer stream, the catalyst feed or with any other component, or may be added alone.

In a preferred embodiment, one or more fluorocarbons are added to a polymerization process in a polymerization reactor in an amount effective to reduce the viscosity of the polymerization medium or effluent by 10 centipoise, preferably by at least 25 centipoise, more preferably at least 50 centipoise, more preferably at least 100 centipoise, more preferably at least 500 centipoise, more preferably at least 1000 centipoise, more preferably at least 2000 centipoise as compared to the exact same polymerization medium or effluent without the fluorocarbon.

In a preferred embodiment, one or more fluorocarbons are added to a polymerization process in a polymerization reactor in an amount effective to reduce the viscosity of the polymerization medium or effluent by at least 3%, preferably by at least 5%, preferably by at least 10%, more preferably at least 15%, more preferably at least 20% as compared to the exact same polymerization medium or effluent without the fluorocarbon. The viscosity of the polymerization medium or the effluent is measured using a rotational viscometer developed by Geerissen, H., F. Gemandt, B. A. Wolf, and H. Lentz (“Pressure dependence of viscometric relaxation times measured with a new apparatus-WLF behavior of moderately concentrated solutions of poly(n-butylmethacrylate)s in 2-propanol,” Makromol. Chem. 192, 165-176, 1991). The apparatus consists of a measuring head and a high-pressure cell which is designed for a maximum pressure of 320 MPa. The cylindrical mantle has a height of 150 mm and an outside diameter of 100 mm. The main part contains a rotor that can be moved in a coaxial stator. The stator has an inside diameter of 35.24 mm and is fixed in a holder. The height of the rotor is 58 mm, and the outside diameter is 35.05 mm. The high-pressure cell is sealed by an O-ring placed between the holder and the outside mantle. To drive the rotor, a measuring head is arranged above the cell. A motor at its top generates torque which is transmitted to the lower cylinder via a shaft. The cylinder contains permanent magnets that have counterparts inside the rotor. Through the antimagnetic holder rotational movement is transferred. The maximum shear stress achievable without slippage of the magnetic coupling is 420 Pa. The polymer sample is first dissolved in a solvent at a given concentration, and the polymer solution is homogenized in an autoclave reactor. After homogenizing the polymer solution, it is fed into an electrically heated viscometer via a short high-pressure tube. The preset pressure is then adjusted by a metal bellows arranged inside the autoclave. The viscometer is controlled by a computer. Additional torque due to viscous flow of the polymer solution is transmitted to the measuring head and causes drilling of the spring. The angle of drilling is used to determine the torque from which the dynamic viscosity is calculated.

In another embodiment, this invention relates to a method to increase the amount of polymer solute present in a polymerization medium or a polymerization effluent by at least 3% (preferably by at least 5%, more preferably by at least 7%, more preferably by at least 10%, more preferably by at least 15%, more preferably by at least 20%) by introducing a fluorocarbon into the polymerization medium or effluent in an amount effective to increase the amount of polymer solute without causing precipitation of the polymer solute, as compared to the exact same medium or effluent without the fluorocarbon. The amount of polymer solute present in a polymerization medium or effluent at a given temperature is determined by separation of the polymer from volatiles in a laboratory evaporation experiment on a small sample of the reaction medium. The testing procedure is described as follows: A small amount (100 ml) of polymerization medium is sampled under the reaction condition into a stainless steel vessel of known weight. The sample vessel is then weighed to obtain the amount of polymerization medium sampled. The sample is discharged into an open container placed in a hood to evaporate the solvent and unreacted monomer. The separated polymer is further dried in a vacuum oven at 90° C. for about 12 hours. The vacuum oven dried samples is weighed to obtain the amount of polymer in the polymer solute. The weight % polymer solute present=[(the weight of the dry polymer)/(the weight of the reaction medium)]×100.

In a preferred embodiment, the polymerization process is one where the monomer(s) to be polymerized are used as the reaction medium (regardless of whether the monomers act as solvent or diluent) and one or more fluorocarbons are added to the polymerization reactor in an amount effective to increase the polymer solute present in a polymerization medium or a polymerization effluent by at least 3% (preferably by at least 5%, more preferably by at least 7%, more preferably by at least 10%, more preferably by at least 15%, more preferably by at least 20%) without causing precipitation of the polymer solute, as compared to the exact same medium or effluent without the fluorocarbon. Alternatively or additionally, the polymerization process is one where the monomer(s) to be polymerized are used as the reaction medium (regardless of whether the monomers act as solvent or diluent) and one or more fluorocarbons are added to the polymerization reactor in an amount effective to reduce the viscosity of the medium or effluent by at least 3%, preferably by at least 5%, preferably by at least 10%, more preferably at least 15%, more preferably at least 20% as compared to the exact same polymerization medium or effluent without the fluorocarbon.

In a preferred embodiment, the polymerization process is one where the reaction medium comprises a hydrocarbon fluid (regardless of whether the fluid acts as solvent or diluent) and one or more fluorocarbons are added to the polymerization reactor in an amount effective to increase the polymer solute present in a polymerization medium or a polymerization effluent by at least 1%, preferably at least 3% (preferably by at least 5%, more preferably by at least 7%, more preferably by at least 10%, more preferably by at least 15%, more preferably by at least 20%) without causing precipitation of the polymer solute, and or in an amount effective to reduce the viscosity of the medium or effluent by at least 3%, preferably by at least 5%, preferably by at least 10%, more preferably at least 15%, more preferably at least 20% as compared to the exact same medium or effluent without the fluorocarbon. Preferably, the hydrocarbon solvent is an aliphatic or aromatic hydrocarbon. Examples of suitable, preferably inert, solvents include, for example, saturated hydrocarbons containing from 3 to 8 carbon atoms, such as propane, n-butane, isobutane, cyclopentane, n-pentane, isopentane, neopentane, n-hexane, isohexane, cyclohexane, and other saturated C ₆ to C ₈ hydrocarbons.

In a preferred embodiment the fluorocarbons are added in an amount effective to reduce the viscosity of the polymerization medium or effluent by 10 centipoise, preferably by at least 200 centipoise, more preferably at least 300 centipoise, more preferably at least 500 centipoise without causing precipitation of the polymer solute, as compared to the exact same medium or effluent without the fluorocarbon.

In a preferred embodiment the fluorocarbons are added in an amount effective to increase the polymer solute present in a polymerization medium or a polymerization effluent by 1 to 50%, preferably by 3 to 45%, more preferably by 5 to 40%, more preferably by 10 to 35%, more preferably by 15 to 30%, more preferably by 20 to 30% without causing precipitation of the polymer solute, as compared to the exact same medium or effluent without the fluorocarbon.

In a preferred embodiment the fluorocarbons are added in an amount effective to reduce the viscosity of the medium or effluent by at least 5%, preferably by at least 10%, more preferably at least 15%, more preferably at least 20% without causing precipitation of the polymer solute, as compared to the exact same medium or effluent without the fluorocarbon.

By the phrase “without causing precipitation of the polymer solute” is meant that the fluorocarbon does not cause precipitation of polymer out of solution or if it does cause a minor amount of precipitation, that it is insignificant enough to not cause fouling in the selected reactor system. In particular the phrase “without causing precipitation of the polymer solute” means that the fluorocarbon does not cause precipitation of more than 1 weight % polymer out of solution, preferably that the fluorocarbon does not cause precipitation of more than 0.5 weight % polymer out of solution, preferably that the fluorocarbon does not cause precipitation of more than 0.1 weight % polymer out of solution, preferably that the fluorocarbon does not cause precipitation of more than 0.01 weight % polymer out of solution, preferably that the fluorocarbon does not cause precipitation of more than 0.001 weight % polymer out of solution. Amount of polymer (weight %) precipitate present in a polymerization medium or effluent is determined by measuring the intensity of a transmitted light of the polymer solution at polymerization reaction condition. Presence of polymer precipitates causes light intensity decay. The ratio of light intensity transmitted through polymerization medium with presence of polymer precipitates to the light intensity transmitted through the polymerization medium without polymer precipitate is correlated to the concentration of polymer precipitates in the reaction medium.

In a preferred embodiment, the fluorocarbons are present in the polymerization medium at 1 to 50 volume %, based upon the volume of the medium, preferably the fluorocarbons are present at 5 to 40 volume %, preferably 5 to 30 volume %, more preferably at 10 to 30 volume %, more preferably 10 to 20 volume %. In a preferred embodiment, the fluorocarbon is present in the polymerization medium at 0.1 to 20 volume %, more preferably 1 to 15 volume %, more preferably 5 to 10 volume %. For purposes of this invention and the claims thereto polymerization medium means the mixture of solvent, unreacted monomers, polymer produced.

In a preferred embodiment, the fluorocarbons are present in the polymerization effluent at 1 to 50 volume %, based upon the volume of the medium, preferably the fluorocarbons are present at 5 to 40 volume %, preferably 5 to 30 volume %, more preferably at 10 to 30 volume %, more preferably 10 to 20 volume %. In a preferred embodiment, the fluorocarbons are present in the polymerization effluent at 0.1 to 20 volume %, based upon the volume of the effluent, preferably the fluorocarbons are present at 1 to 15 volume %, preferably 2 to 15 volume %, more preferably at 5 to 15 volume %. For purposes of this invention and the claims thereto polymerization effluent means the mixture exiting the reactor and all additives added to it until the first flash or solvent removal step.

Fluorocarbons

The polymerization processes of this invention are preferably conducted in the presence of a perfluorocarbon (“PFC” or “PFC's”) or a hydrofluorocarbon (“HFC” or “HFC's”), collectively referred to as “fluorinated hydrocarbons” or “fluorocarbons” (“FC” or “FC's”). In another embodiment the polymerization process is conducted without fluorocarbon present and the fluorocarbon is added to the polymerization effluent after the polymerization reaction has stopped. In another embodiment the polymerization process is conducted without fluorocarbon present and the fluorocarbon is added to the polymerization effluent after the polymerization effluent has exited the reactor. In another embodiment the polymerization process is conducted in the presence of fluorocarbon and additional fluorocarbon (which may be the same or different from the first fluorocarbon) is added to the polymerization effluent after the polymerization reaction has exited the reactor and or the polymerization reaction has stopped.

Fluorocarbons are defined to be compounds consisting essentially of at least one carbon atom and at least one fluorine atom, and optionally hydrogen atom(s). A perfluorocarbon is a compound consisting essentially of carbon atom and fluorine atom, and includes for example linear branched or cyclic, C ₁ to C ₄₀ perfluoroalkanes. A hydrofluorocarbon is a compound consisting essentially of carbon, fluorine and hydrogen. Preferred HFC's include those represented by the formula: C _x H _y F _z wherein x is an integer from 1 to 40, alternatively from 1 to 30, alternatively from 1 to 20, alternatively from 1 to 10, alternatively from 1 to 6, alternatively from 2 to 20 alternatively from 3 to 10, alternatively from 3 to 6, most preferably from 1 to 3, wherein y is greater than or equal 0 and z is an integer and at least one, more preferably, y and z are integers and at least one. In a preferred embodiment z is 2 or more. For purposes of this invention and the claims thereto, the terms hydrofluorocarbon and fluorocarbon do not include chlorofluorocarbons.

In one embodiment, a mixture of fluorocarbons are used in the process of the invention, preferably a mixture of a perfluorinated hydrocarbon and a hydrofluorocarbon, and more preferably a mixture of a hydrofluorocarbons. In another embodiment, the fluorocarbon is not a perfluorinated hydrocarbon. In yet another embodiment, the hydrofluorocarbon is balanced or unbalanced in the number of fluorine atoms in the HFC used.

Non-limiting examples of fluorocarbons useful in this invention include 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; 1,1,2,2,3,3,4-heptafluorocyclobutane. In addition to those fluorocarbons described herein, those fluorocarbons described in Raymond Will, et. al., CEH Marketing Report, Fluorocarbons, Pages 1-133, by the Chemical Economics Handbook-SRI International, April 2001, which is fully incorporated herein by reference, are included.

In another preferred embodiment, the fluorocarbon(s) used in the process of the invention are selected from the group consisting of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, and 1,1,1,2-tetrafluoroethane and mixtures thereof.

In one particularly preferred embodiment, the commercially available fluorocarbons useful in the process of the invention include HFC-236fa having the chemical name 1,1,1,3,3,3-hexafluoropropane, HFC-134a having the chemical name 1,1,1,2-tetrafluoroethane, HFC-245fa having the chemical name 1,1,1,3,3-pentafluoropropane, HFC-365mifc having the chemical name 1,1,1,3,3-pentafluorobutane, R-318 having the chemical name octafluorocyclobutane, and HFC-43-10mee having the chemical name 2,3-dihydrodecafluoropentane.

In another embodiment, the fluorocarbon is not a perfluorinated C4 to C10 alkane. In another embodiment, the fluorocarbon is not perfluorodecalin, perfluoroheptane, perfluorohexane, perfluoromethylcyclohexane, perfluorooctane, perfluoro-1,3-dimethylcyclohexane, perfluorononane, fluorobenzene, or perfluorotoluene. In a particularly preferred embodiment, the fluorocarbon consists essentially of hydrofluorocarbons.

In another embodiment the fluorocarbon is present at more than 1 weight %, based upon the weight of the fluorocarbon and any hydrocarbon solvent present in the reactor, preferably greater than 3 weight %, preferably greater than 5 weight %, preferably greater than 7 weight %, preferably greater than 10 weight %, preferably greater than 15 weight %, preferably greater than 20 weight %, preferably greater than 25 weight %, preferably greater than 30 weight %, preferably greater than 35 weight %, preferably greater than 40 weight %, preferably greater than 50 weight %, preferably greater than 55 weight %, preferably greater than 60 weight %, preferably greater than 70 weight %, preferably greater than 80 weight %, preferably greater than 90 weight %. In another embodiment the fluorocarbon is present at more than 1 weight %, based upon the weight of the fluorocarbons, monomers and any hydrocarbon solvent present in the reactor, preferably greater than 3 weight %, preferably greater than 5 weight %, preferably greater than 7 weight %, preferably greater than 10 weight %, preferably greater than 15 weight %, preferably greater than 20 weight %, preferably greater than 25 weight %, preferably greater than 30 weight %, preferably greater than 35 weight %, preferably greater than 40 weight %, preferably greater than 50 weight %, preferably greater than 55 weight %, preferably greater than 60 weight %, preferably greater than 70 weight %, preferably greater than 80 weight %, preferably greater than 90 weight %. In the event that the weight basis is not named for the weight % fluorocarbon, it shall be presumed to be based upon the total weight of the fluorocarbons, monomers and hydrocarbon solvents present in the reactor.

In another embodiment the fluorocarbon, preferably the hydrofluorocarbon, is present at more than 1 volume %, based upon the total volume of the fluorocarbon and any hydrocarbon solvent present in the reactor, preferably greater than 3 volume %, preferably greater than 5 volume %, preferably greater than 7 volume %, preferably greater than 10 volume %, preferably greater than 15 volume %, preferably greater than 20 volume %, preferably greater than 25 volume %, preferably greater than 30 volume %, preferably greater than 35 volume %, preferably greater than 40 volume %, preferably greater than 45 volume %, preferably greater than 50 volume %, preferably greater than 55 volume %, preferably greater than 60 volume %, preferably greater than 65 volume %.

In another embodiment the fluorocarbon is a blend of hydrofluorocarbon and perfluorocarbon and preferably the hydrofluorocarbon is present at more than 1 volume %, based upon the total volume of the perfluorocarbon and the hydrofluorocarbon present in the reactor, (with the balance being made up by the perfluorocarbon) preferably greater than 3 volume %, preferably greater than 5 volume %, preferably greater than 7 volume %, preferably greater than 10 volume %, preferably greater than 15 volume %, preferably greater than 20 volume %, preferably greater than 25 volume %, preferably greater than 30 volume %, preferably greater than 35 volume %, preferably greater than 40 volume %, preferably greater than 45 volume %, preferably greater than 50 volume %, preferably greater than 55 volume %, preferably greater than 60 volume %, preferably greater than 65 volume %.

In yet another embodiment, the fluorocarbons of the invention have a weight average molecular weight (Mw) greater than 30 a.m.u., preferably greater than 35 a.m.u, and more preferably greater than 40 a.m.u. In another embodiment, the fluorocarbons of the invention have a Mw greater than 60 a.m.u, preferably greater than 65 a.m.u, even more preferably greater than 70 a.m.u, and most preferably greater than 80 a.m.u. In still another embodiment, the fluorocarbons of the invention have a Mw greater than 90 a.m.u, preferably greater than 100 a.m.u, even more preferably greater than 135 a.m.u, and most preferably greater than 150 a.m.u. In another embodiment, the fluorocarbons of the invention have a Mw greater than 140 a.m.u, preferably greater than 150 a.m.u, more preferably greater than 180 a.m.u, even more preferably greater than 200 a.m.u, and most preferably greater than 225 a.m.u. In an embodiment, the fluorocarbons of the invention have a Mw in the range of from 90 a.m.u to 1000 a.m.u, preferably in the range of from 100 a.m.u to 500 a.m.u, more preferably in the range of from 100 a.m.u to 300 a.m.u, and most preferably in the range of from about 100 a.m.u to about 250 a.m.u.

In yet another embodiment, the fluorocarbons of the invention have normal boiling point in the range of from about −100° C. up to the polymerization temperature, preferably up to about 70° C., preferably up to about 85 to 115° C., preferably the normal boiling point of the fluorocarbons is in the range of from −80° C. to about 90° C., more preferably from about −60° C. to about 85° C., and most preferably from about −50° C. to about 80° C. In an embodiment, the fluorocarbons of the invention have normal boiling point greater than −50° C., preferably greater than −50° C. to less than −10° C. In a further embodiment, the fluorocarbons of the invention have normal boiling point greater than −5° C., preferably greater than −5° C. to less than −20° C. In one embodiment, the fluorocarbons of the invention have normal boiling point greater than 10° C., preferably greater than 10° C. to about 60° C.

In another embodiment, the fluorocarbons of the invention have a liquid density @ 20° C. (g/cc) less than 2 g/cc, preferably less than 1.6, preferably less than 1.5 g/cc, preferably less than 1.45 g/cc, preferably less than 1.40, and most preferably less than 1.20 g/cc.

In one embodiment, the fluorocarbons of the invention have a ΔH Vaporization at the normal boiling point as measured by standard calorimetry techniques in the range between 100 kJ/kg to less than 500 kJ/kg, preferably in the range of from 110 kJ/kg to less than 450 kJ/kg, and most preferably in the range of from 120 kJ/kg to less than 400 kJ/kg.

In another preferred embodiment, the fluorocarbons of the invention have any combination of two or more of the aforementioned Mw, normal boiling point, ΔH Vaporization, and liquid density values and ranges. In a preferred embodiment, the fluorocarbons useful in the process of the invention have a Mw greater than 30 a.m.u, preferably greater than 40 a.m.u, and a liquid density less than 2.00 g/cc, preferably less than 1.8 g/cc. In yet another preferred embodiment, the fluorocarbons useful in the process of the invention have a liquid density less than 1.9 g/cc, preferably less than 1.8 g/cc, and a normal boiling point greater than −100° C., preferably greater than −50° C. up to the polymerization temperature of the process, (such as up to 115° C.), preferably less than 100° C., and more preferably less than 90° C., and most preferably less than 60° C., and optionally a ΔH Vaporization in the range from 120 kj/kg to 400 kj/kg.

In another embodiment the fluorocarbons are used in combination with one or more hydrocarbon solvents. Preferably, the hydrocarbon solvent is an aliphatic or aromatic hydrocarbon fluids. Examples of suitable, preferably inert, solvents include, for example, saturated hydrocarbons containing from 1 to 10, preferably 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, cyclohexane and other saturated C ₆ to C ₈ hydrocarbons. Preferred hydrocarbon fluids also include desulphurized light virgin naphtha, and alkanes (preferably C1 to C8 alkanes), such as propane, isobutane, mixed butanes, hexane, pentane, isopentane, cyclohexane, isooctane, and octane. Likewise one may also use mixtures of C3 to C20 paraffins and isoparaffins, preferably paraffinic/isoparrifinic mixtures of C4, C5 and or C6 alkanes.

In another embodiment, the FC is selected based upon its solubility or lack thereof in a particular polymer being produced. Preferred fluorocarbons have little to no solubility in the polymer. Solubility in the polymer is measured by forming the polymer into a film of thickness between 50 and 100 microns, then soaking it in fluorocarbon (enough to cover the film) for 4 hours at the relevant desired polymerization temperature and pressure in a sealed container or vessel. The film is removed from the fluorocarbon, exposed for 90 seconds to evaporate excess fluorocarbon from the surface of the film, and weighed. The mass uptake is defined as the percentage increase in the film weight after soaking. The fluorocarbon or fluorocarbon mixture is selected so that the polymer has a mass uptake of less than 4 wt %, preferably less than 3 wt %, more preferably less than 2 wt %, even more preferably less than 1 wt %, and most preferably less than 0.5 wt %.

In a preferred embodiment, the fluorocarbon(s) or mixtures thereof, preferably, the HFC's or mixtures thereof, are selected such that the polymer melting temperature Tm is reduced (or depressed) by not more than 25° C. by the presence of the fluorocarbon, preferably by not more than 20° C., preferably not more than 15° C. The depression of the polymer melting temperature A™ is determined by first measuring the melting temperature of a polymer by differential scanning calorimetry (DSC), and then comparing this to a similar measurement on a sample of the same polymer that has been soaked with the fluorocarbon for four hours. In general, the melting temperature of the soaked polymer will be lower than that of the dry polymer. The difference in these measurements is taken as the melting point depression ΔTm. Higher concentrations of dissolved materials in the polymer cause larger depressions in the polymer melting temperature (i.e. higher values of ΔTm). A suitable DSC technique for determining the melting point depression is described by, P. V. Hemmingsen, “Phase Equilibria in Polyethylene Systems”, Ph.D Thesis, Norwegian University of Science and Technology, March 2000, which is incorporated herein by reference. (A preferred set of conditions for conducting the tests are summarized on Page 112 of this reference.) The polymer melting temperature is first measured with dry polymer, and then repeated with the polymer immersed in liquid (the fluorocarbon to be evaluated). As described in the reference above, it is important to ensure that the second part of the test, conducted in the presence of the liquid, is done in a sealed container so that the liquid is not flashed during the test, which could introduce experimental error. In one embodiment, the A™ is less than 12° C., preferably less than 10° C., preferably less than 8° C., more preferably less than 6° C., and most preferably less than 4° C. In another embodiment, the measured A™ is less than 5° C., preferably less than 4° C., more preferably less than 3° C., even more preferably less than 2° C., and most preferably less than 1° C.

In a preferred embodiment, the fluorocarbon(s) or mixtures thereof, preferably, the fluorocarbon or mixtures thereof, are selected such that these are miscible to the hydrocarbon solvent and liquid monomers when a mixture is used. By miscible is meant that the FC and the hydrocarbon mixture will not have liquid phase separation. Liquid phase separation is determined by mixing a fluorocarbon and a hydrocarbon in a vessel with sight glass at polymerization conditions, then visually observing if phase separation occurs after vigorous mixing for five minutes.

Ideally, the fluorocarbon is inert to the polymerization reaction. By “inert to the polymerization reaction” is meant that the fluorocarbon does not react chemically with the, monomers, catalyst system or the catalyst system components. (This is not to say that the physical environment provided by an FC's does not influence the polymerization reactions, in fact, it may do so to some extent, such as affecting activity rates. However, it is meant to say that the FC's are not present as part of the catalyst system.)

Polymerization Process

For purposes of this invention and the claims thereto, by continuous is meant a system that operates (or is intended to operate) without interruption or cessation. For example a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

In a preferred embodiment any of the polymerization process described herein are a continuous process.

In a preferred embodiment, the catalyst systems described herein are used in a polymerization process to produce olefin polymers, particularly ethylene and or propylene based olefin polymers where the polymer is produced such that it is present as a solute in the polymerization medium or polymerization effluent. Generally this involves polymerization in a continuous reactor in which the polymer formed and the starting monomer and catalyst materials supplied, are agitated to reduce or avoid concentration gradients and in which the monomer acts as diluent or solvent or in which a hydrocarbon is used as a diluent or solvent. Suitable processes typically operate at temperatures from 0 to 350° C., preferably from 10 to 300° C., more preferably from 40 to 250, more preferably 50 to 235° C. and preferably at pressures of 0.1 MPa or more, preferably 2 MPa or more. In another embodiment, the polymerization temperature is above room temperature (23° C.), preferably above 30° C., preferably above 50° C., preferably above 70° C. The upper pressure limit is not critically constrained but typically can be 200 MPa or less, preferably, 120 MPa or less. Temperature control in the reactor is generally obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds may also be used. Preferably a fluorocarbon is added to the polymerization reactor as a pure component or a mixture with other fluorocarbon and/or hydrocarbon. The type and amount of fluorocarbon in a mixture with hydrocarbon is such that precipitation of polymers produced does not occur when a mixture of fluorocarbon and hydrocarbon is used. The type and amount of fluorocarbon is also preferably optimized for the maximum catalyst productivity for a particular type of polymerization. The fluorocarbon can be also introduced into the reactor as a catalyst carrier. The fluorocarbon can be introduced as a gas phase or as a liquid phase depending on pressure and temperature. Advantageously, the fluorocarbon is kept in a liquid phase and introduced as a liquid. FC can be introduced in the feed to the polymerization reactors or in the polymerization reactor effluent.

In a preferred embodiment, the polymerization process is a steady state, polymerization conducted in a well-mixed continuous feed polymerization reactor or reactors in series or parallel configuration. A preferred process can be described as a continuous, non-batch process that, in its steady state operation, is exemplified by removal of amounts of polymer made per unit time, being substantially equal to the amount of polymer withdrawn from the reaction vessel per unit time. By “substantially equal” is meant that these amounts, polymer made per unit time, and polymer withdrawn per unit time, are in ratios of one to the other, of from 0.9:1; or 0.95:1; or 0.97:1; or 1:1. In such a reactor, there is preferably a substantially homogeneous monomer distribution. At the same time, the polymerization is accomplished in substantially single step or stage or in a single reactor, contrasted to multistage or multiple reactors (two or more). These conditions preferably exist for substantially all of the time the copolymer is produced. In such a process the fluorocarbon is preferably injected into the first reactor feed however the FC may also be injected into the reactor(s) directly

In another preferred embodiment, the following procedure is carried out to obtain a copolymer, preferably comprising propylene and ethylene. In a stirred-tank reactor propylene monomer is introduced continuously together with solvent (if any), fluorocarbon and ethylene monomer. The reactor contains a liquid phase composed substantially of fluorocarbon, and ethylene and propylene monomers together with any solvent or additional diluent. If desired, a small amount of a “H”-branch inducing diene such as norbornadiene, 1,7octadiene or 1,9-decadiene may also be added. A transition metal compound and activator are continuously introduced in the reactor liquid phase. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by cooling or heating coils, jackets or both. Preferably the polymerization rate is controlled by the rate of catalyst addition. Typically, the ethylene content of the polymer product can be determined by the ratio of ethylene to propylene in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is preferably controlled by controlling other polymerization variables such as the temperature, monomer concentration, or by a stream of hydrogen introduced to the reactor, as is known in the art. The reactor effluent is optionally contacted with a catalyst kill agent, such as water. The polymer solution is then optionally heated, and the polymer product is recovered by flashing off unreacted gaseous ethylene and propylene and fluorocarbon as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting farther devolatilization in equipment such as a devolatilizing extruder or other devolatilizing equipment operated at reduced pressure.

For a propylene homo- or co-polymerization process conducted in the presence of hydrocarbon diluent or solvent in addition to the fluorocarbon, especially a continuous polymerization, preferred ranges of propylene concentration at steady state are from about 0.05 weight percent of the total reactor contents to about 50 weight percent of the total reactor contents, more preferably from about 0.5 weight percent of the total reactor contents to about 30 weight percent of the total reactor contents, and most preferably from about 1 weight percent of the total reactor contents to about 25 weight percent of the total reactor contents. The preferred range of polymer concentration (otherwise known as % solids) is from about 3% of the reactor contents by weight to about 45% of the reactor contents or higher, more preferably from about 10% of the reactor contents to about 40% of the reactor contents, and most preferably from about 15% of the reactor contents to about 40% of the reactor contents.

Preferably in a continuous process, the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours, more preferably from ten minutes to one hour. In some embodiments, comonomer (such as ethylene) is added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the main monomer (such as a propylene) and any optional diene monomers present.

In another embodiment, the polymerization process is carried out with a pressure of ethylene of from 10 to 2000 psi (70 to 14000 kPa), most preferably from 40 to 950 psi (275 to 6500 kPa). The polymerization is generally conducted at a temperature of from 25 to 350° C., preferably from 75 to 300° C., and most preferably from greater than 95 to 250° C.

In another preferred embodiment, a process for producing a propylene homopolymer or copolymer of propylene with at least one additional olefinic monomer selected from ethylene or C4 to C20 alpha-olefins comprises the following steps: 1) providing controlled addition of a transition metal compound to a reactor, including an activator and optionally a scavenger component; 2) continuously feeding propylene and optionally one or more additional olefinic monomers independently selected from ethylene or C4 to C20 alpha-olefins into the reactor, optionally with a solvent or diluent, and optionally with a controlled amount of hydrogen; 3) feeding fluorocarbon into the polymerization reactor; and 4) recovering the polymer product. Preferably, the process is a continuous process that may or may not have hydrocarbon solvent or diluent present in the reaction medium. Preferred ranges of ethylene concentration at steady state are from less than about 0.02 weight percent of the total reactor contents to about 5 weight percent of the total reactor contents, and the preferred range of polymer concentration is from about 10% of the reactor contents by weight to about 45% of the reactor contents or higher. The activators and optional scavenger components in the process can be independently mixed with the catalyst component before introduction into the reactor, or they may each independently be fed into the reactor using separate streams, resulting in “in reactor” activation. Scavenger components are known in the art and include, but are not limited to, alkyl aluminum compounds, including alumoxanes. Examples of scavengers include, but are not limited to, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, methylalumoxane (MAO), and other alumoxanes including, but not limited to, MMAO3A. MMAO-7, PMAO-IP (all available from Akzo Nobel). Likewise, the fluorocarbons may be introduced into the reactor as a mixture with one or more catalyst system components or a scavenger.

In another preferred embodiment, a process for producing an ethylene homopolymer or copolymer of ethylene with at least one additional olefinic monomer selected from C3 to C20 alpha-olefins comprises the following steps: 1) providing controlled addition of a transition metal compound to a reactor, including an activator and optionally a scavenger component; 2) continuously feeding ethylene and optionally one or more additional olefinic monomers independently selected from C3 to C20 alpha-olefins into the reactor, optionally with a solvent or diluent, and optionally with a controlled amount of hydrogen; 3) feeding fluorocarbon into the polymerization reactor; and 4) recovering the polymer product. Preferably, the process is a continuous process that may or may not have hydrocarbon solvent or diluent present in the reaction medium. Preferred ranges of comonomer concentration at steady state are from less than about 0.02 weight percent of the total reactor contents to about 15 weight percent of the total reactor contents, and the preferred range of polymer concentration is from about 10% of the reactor contents by weight to about 45% of the reactor contents or higher. The activators and optional scavenger components in the process can be independently mixed with the catalyst component before introduction into the reactor, or they may each independently be fed into the reactor using separate streams, resulting in “in reactor” activation. Scavenger components are known in the art and include, but are not limited to, alkyl aluminum compounds, including alumoxanes. Examples of scavengers include, but are not limited to, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, methylalumoxane (MAO), and other alumoxanes including, but not limited to, MMAO3A. MMAO-7, PMAO-IP (all available from Akzo Nobel). Likewise, the fluorocarbons may be introduced into the reactor as a mixture with one or more catalyst system components or a scavenger.

The processes described herein can be carried out in a continuous stirred tank reactor, batch reactor, or plug flow reactor, or more than one reactor operated in series or parallel. These reactors may have or may not have internal cooling and the monomer feed may or may not be refrigerated. See the general disclosure of U.S. Pat. No. 5,001,205 for general process conditions. See also, international application WO 96/33227 and WO 97/22639. As previously noted, the processes described above may optionally use more than one reactor. The use of a second reactor is especially useful in those embodiments in which an additional catalyst, especially a Ziegler-Natta or chrome catalyst, or by proper selection of process conditions, including catalyst selection, polymers with tailored properties can be produced. The cocatalysts and optional scavenger components in the process can be independently mixed with the catalyst component before introduction into the reactor, or they may each independently be fed into the reactor using separate streams, resulting in “in reactor” activation. Likewise, the fluorocarbons may be introduced into the reactor as a mixture with one or more catalyst system components or a scavenger. Each of the above processes may be employed in single reactor, parallel or series reactor configurations. In series operation, the second reactor temperature is preferably higher than the first reactor temperature. In parallel reactor operation, the temperatures of the two reactors are independent. The pressure can vary from about 1 mm Hg to 2500 bar (250 MPa), preferably from 1 bar to 1600 bar (0.1-160 MPa), most preferably from 1 to 500 bar (0.1-50 MPa). The liquid processes comprise contacting olefin monomers with the above described catalyst system in a suitable diluent or solvent and allowing said monomers to react for a sufficient time to produce the desired polymers. In multiple reactor processes the fluorocarbon may be introduced into one or all of the reactors. In particular, a fluorocarbon can be introduced into the first reactor, and a second fluorocarbon (which may be the same or different from the first fluorocarbon) may be introduced into the second reactor. Likewise the fluorocarbon may be introduced in the first reactor alone or the second reactor alone. In addition to the above, in multiple reactor configurations where there is a third, fourth or fifth reactor, the fluorocarbon may be introduced into all of the third, fourth and fifth reactors, none of the third, fourth and fifth reactors, just the third reactor, just the fourth reactor, just the fifth reactor, just the third and fourth reactors, just the third and fifth reactors, or just the fourth and fifth reactors.

Hydrocarbon fluids are suitable for use in the polymerizations of this invention as reaction medium or parts of reaction medium. Preferred hydrocarbon fluids include both aliphatic and aromatic fluids, such as desulphurized light virgin naphtha, and alkanes, such as propane, isobutane, mixed butanes, hexane, pentane, isopentane, isooctane, cyclohexane, isooctane and octane. Likewise one may also use mixtures of C3 to C20 paraffins and isoparaffins, preferably paraffinic/isoparrifinic mixtures of C4, C5 and or C6 alkanes.

In a preferred embodiment, a continuous solution polymerization is used to produce copolymers of propylene and butene and or hexene. The copolymer may also optionally contain diene and or up to 10 weight % ethylene. The polymerization process utilizes two or more metallocene catalysts as described below, preferably, dimethylsilyl tetramethylcyclopentadienyl dodecylamide titanium dimethyl, rac-dimethylsilyl bis(2-methyl-4-phenyl indenyl)zirconium dimethyl, 1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl )(2,7-di-tertiary-butyl-9-fluorenyl)hafnium dimethyl, and or dimethylsilylbis(indenyl)hafnium dimethyl; combined with dimethylaniliniumtetrakis-(perfluorophenyl)borate as an activator. An organoaluminum compound, namely, tri-n-octylaluminum, tri-isobutyl aluminum and or triethyl aluminum is preferably added as a scavenger to the monomer feedstreams prior to introduction into the polymerization process. The solution polymerization is conducted in a single, or optionally in two, continuous stirred tank reactors connected in series with hexane, pentane or Isoparm used as the solvent. The reactors may be operated adiabatically or with a cooling loop. In addition, toluene may be added to increase the solubility of the co-catalyst. The catalysts in hexane and the activator in toluene are introduced into the reactor or are introduced into the feed line and are mixed in line for a short time prior to being fed into the reactor. The feed is transferred to the first reactor where the exothermic polymerization reaction is conducted adiabatically or with a coolant loop at a reaction temperature between about 50° C. to about 220° C. The coolant loop, if present is, typically kept at a temperature within 20° C. below the reactor temperature. Hydrogen gas may also be added to the reactors as a further molecular weight regulator. Scavenger (such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum) may be used if desired. If desired, polymer product is then transferred to a second reactor, which is also operated adiabatically or with a coolant loop at a temperature between about 50° C. to 200° C. Additional monomers, solvent, catalyst, and activators can be fed to the second reactor. The polymer content leaving the reactor(s) is typically from 8 to 50 weight percent. A heat exchanger then heats the polymer solution to a temperature of about 220° C. The polymer solution enters a low pressure separator vessel which operates at a temperature of about 200-230° C. and a pressure of 0-10 bar (1000 kPa) and flashes the polymer solution to remove volatiles and to increase the polymer content to about 76 to about 98 wt. %. The polymer rich solution is then quenched with water, a low boiling alcohol or another oxygenated hydrocarbon such as a fatty acid (such as stearic acid, or a metal salt thereof). The volatiles from the flash vessel may then be recirculated to the reactor(s). A gear pump at the bottom of the flash vessel drives the polymer rich solution to a flash devolatilizer. An gear pump is coupled to the end of the flash devolatizer whereby the molten polymer material is transferred to a static mixer where additives (e.g. 0-20 wt % tackifier, 0-20 wt % oil, 0-20 wt % LMWiPP, 0.1 to 10 wt % antioxidant, 0 to 10 wt % stabilizer, 0-10 wt % wax, 0-10 wt % maleated PP wax) are combined with the molten polymer. Then the molten polymer may be fed to underwater pelletizer where is cut into pellets, or the molten polymer may be packaged in drum containers. A spin dryer dries the polymer pellets which have a final solvent content of less than about 0.5 wt. %. Preferably a controlled volume of FC component(s) is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors. The range of FC's used is guided by a combination of:

a) The boiling point of the FC is preferably higher than ethylene and propylene so that the FC will co-condense and recycle with the hydrocarbon solvent, if any (typically hexanes), preferably the boiling point is in the range of from 0 to 70° C.; and or

b) The extent of fluorination of the FC's is such that they form a single phase with the hydrocarbon solvent (preferably hexane) but are present in a controlled quantity to avoid polymer precipitation in the polymerization reactors, reactor effluent preheater and first flash vessel at operating conditions. Their impact on polymer solvation and hydrodynamic volume is such that the viscosity of an FC modified solution is lower than that without FC for the same polymer molecular weight and concentration.

In another preferred embodiment, a continuous solution polymerization process is used to produce copolymers of ethylene/octene or ethylene/propylene or terpolymers of ethylene/propylene/diene, preferably polymers of propylene and from 0.5 to 20 weight % ethylene. For plastomers and elastomers the polymerization process preferably utilizes a metallocene catalyst, namely, 1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl )(2,7-di-tertiary-butyl-9-fluorenyl)hafnium dimethyl with dimethylaniliniumtetrakis(pentafluorophenyl) borate as an activator. An organoaluminum compound, namely, tri-n-octylaluminum, may be added as a scavenger to the monomer feed streams prior to introduction into the polymerization process. For production of more crystalline polymers, dimethylsilylbis(indenyl)hafnium dimethyl is used in combination with dimethylaniliniumtetrakis(pentafluorophenyl) borate. Preferably the solution polymerization is conducted in a single, or optionally in two, continuous stirred tank reactors connected in series with hexane used as the solvent. In addition, toluene may be added to increase the solubility of the co-catalyst. The feed is transferred to the first reactor where the exothermic polymerization reaction is conducted adiabatically at a reaction temperature between about 50° C. to about 220° C. Hydrogen gas may also be added to the reactors as a further molecular weight regulator. If desired, polymer product is then transferred to the second reactor, which is also operated adiabatically at a temperature between about 50° C. to 200° C. Additional monomers, solvent, metallocene catalyst, and activators can be fed to the second reactor. The polymer content leaving the second reactor is preferably from 8 to 22 weight percent. A heat exchanger then heats the polymer solution to a temperature of about 220° C. The polymer solution is then brought to a Lower Critical Solution Temperature (LCST) liquid-liquid phase separator which causes the polymer solution to separate into two liquid phases—an upper lean phase and a lower polymer-rich phase. The upper lean phase contains about 70 wt. % of the solvent and the lower polymer rich phase contains about 30 Wt. % polymer. The polymer solution then enters a low pressure separator vessel which operates at a temperature of about 150° C. and a pressure of 4-10 barg (400 to 1000 kPa) and flashes the lower polymer rich phase to remove volatiles and to increase the polymer content to about 76 wt %, preferably up to a