WO2006002132A2 - Procede de polymerisation - Google Patents

Procede de polymerisation Download PDF

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Publication number
WO2006002132A2
WO2006002132A2 PCT/US2005/021865 US2005021865W WO2006002132A2 WO 2006002132 A2 WO2006002132 A2 WO 2006002132A2 US 2005021865 W US2005021865 W US 2005021865W WO 2006002132 A2 WO2006002132 A2 WO 2006002132A2
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WIPO (PCT)
Prior art keywords
reactor
polymer
polymerization
catalyst
weight
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PCT/US2005/021865
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English (en)
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WO2006002132A3 (fr
Inventor
Peijun Jiang
John R. Shutt
Charles S. Speed
Robert O. Hagerty
Pradeep P. Shirodkar
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Exxonmobil Chemical Patents Inc.
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Priority to US11/628,165 priority Critical patent/US7799882B2/en
Publication of WO2006002132A2 publication Critical patent/WO2006002132A2/fr
Publication of WO2006002132A3 publication Critical patent/WO2006002132A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Definitions

  • This invention relates to the use of a fluorocarbon in an olefin polymerization process with a homogeneous catalyst or catalyst system at a temperature below the melting point of the polymer being produced.
  • Unsaturated monomers are polymerized in a variety of polymerization processes using a wide variety of catalysts and catalyst systems.
  • One of the most common polymerization process used in the production of olefin based polymers such as polyethylene or polypropylene (homopolymers as well as copolymers) is a solution based process, hi such a process the formed polymer is dissolved in the polymerization medium.
  • the catalyst and monomer are also dissolved in the polymerization medium, but that is not a requirement of a "solution” process.
  • the polymerization temperature may be at, above or below the melting point of the dry polymer.
  • 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.
  • solvents or diluents are used, while in others the monomer to be polymerized also acts as the solvent (e.g. a bulk process).
  • solvents or diluents are used, while in others the monomer to be polymerized also acts as the solvent (e.g. a bulk process).
  • solvent e.g. a bulk process
  • the polymer formed is dissolved in the solvent. The higher the concentration of the polymer, the higher the viscosity of the polymerization reaction mixture containing polymer, monomers and solvent.
  • the polymer concentration is limited by viscosity for easy handling and process economics. This is especially true for polymers with high molecular weight.
  • An alternative to a solution process is the slurry process in which the polymer product forms a slurry rather than a solution in the polymerization medium. Viscosity in a slurry reactor, is lower due to the formation of polymer particles in the reaction medium. Ih such situations, the viscosity of the polymer slurry does not increases as rapidly as the polymer concentration increases and therefore polymer concentration (or loading) can be increased up to 40% as compared with less than 20% in solution process.
  • Slurry processes also facilitate the production of high molecular weight polymers ( >100 Mooney viscosity) due to the nature of low viscosity as compared to that in solution reactors. Moreover, there is less solvent to remove and the quantity of recycled solvent is reduced considerably in a slurry process. Polymers with low crystallinity or low melting temperature are often produced in a solution process due to the selected operating windows optimized for catalyst and process economics. In the course of finishing, unreacted monomers and solvent are progressively removed from the polymerization mixture until polymer can form solid pellets or bales. Generally polymer solutions can undergo phase separation at the lower critical solution temperature. The phase separation is encouraged by higher temperature and/or lower pressure.
  • the crystallization of polymers leads to polymer-solvent phase separation.
  • polymer- solvent phase separation can be also induced through change of solvency of the reaction medium with respect to the polymer produced.
  • the instant invention provides a process that with proper selection of a fluorinated hydrocarbon or a mixture of fluorinated hydrocarbons and hydrocarbon solvents, the process can be operated in a slurry mode instead of solution. Polymers produced will be in solid- state. Thus the process can produce polymers with a wide range of crystallinity or amorphous content.
  • the instant invention also provides a polymerization method that can produce softer polymers (such as ethylene propylene copolymers and terpolymers) that does not require a dusting agent in the reaction medium, unlike some gas- phase process which require partitioning agent such as talc or carbon black.
  • the instant invention also provides a method to prepare ethylene propylene copolymers and terpolymers in granular form (as opposed to crumb/bale form).
  • US Patent 3,470,143 discloses a process to produce a boiling-xylene soluble polymer in a slurry using certain fluorinated organic carbon compounds.
  • US Patent 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 A2 discloses polymerization in polar aprotic solvents, such as halogenated hydrocarbons.
  • US 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.
  • US 5,624,878 discloses the polymerization using "constrained geometry metal complexes" of titanium and zirconium.
  • US 2,534,698, US 2,644,809 and US 2,548,415 disclose preparation of butyl rubber type elastomers in fluorinated solvents.
  • US 6,534,613 discloses use of hydrofluorocarbons as catalyst modifiers.
  • US 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.
  • US 3,056,771 discloses polymerization of ethylene UsUIgTiCV(Et) 3 Al in a mixture of heptane and perfluoromethylcyclohexane, presumably at room temperature. Additional references of interest include: Designing Solvent Solutions, Chemical and Engineering News, October 13, 2004 (www.CEN-online.org); Polymer Synthesis Using Hydrofluorocarbon Solvents., Wood, Colin, et al. Macromolecules, Vol.
  • This invention relates to a polymerization process to produce polyolefins comprising contacting olefins and a homogeneous catalyst or catalyst system in the presence of a fluorinated hydrocarbon at a temperature below the melting point of the dry polymer and above 7O 0 C, where the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the total volume of the mixture of fluorinated hydrocarbon, any hydrocarbon solvent or diluent present and any unreacted monomers present.
  • This invention also relates to a process to produce polyethylene comprising contacting a homogeneous catalyst or catalyst system with ethylene and from 0 to 40 weight % (preferably 0 to 30 wt%, preferably 0 to 20 wt%), based upon the total monomers present, of one or more C3 to C40 olefin comonomer(s) in the presence of a fluorinated hydrocarbon and optionally a hydrocarbon solvent at a temperature below the reaction medium melting point and above 50 0 C, where the fluorinated hydrocarbon is present at more than 5 weight %, based upon the weight of the fluorinated hydrocarbon and any hydrocarbon solvent or diluent present.
  • This invention also relates to a process to produce polypropylene comprising contacting a homogeneous catalyst or catalyst system with propylene and from 0 to 50 weight % of one or more of ethylene and C4 to C40 olefin comonomer(s), based upon the total monomers present, in the presence of a fluorinated hydrocarbon and optionally a hydrocarbon solvent at a temperature below the reaction medium melting point.
  • This invention also relates to a multiple phase (preferably two or more phases) polymerization process to produce polyolefins comprising contacting olefins and a homogeneous catalyst or catalyst system at a temperature between the melting point of the dry polymer and 80 0 C below the melting point of the dry polymer (preferably 25 0 C below the melting point of the dry polymer) in the presence of a fluorocarbon.
  • copolymers means any polymer comprising two or more monomers.
  • a polymer is referred to as comprising a monomer
  • the olefin present in the polymer is the polymerized form of the monomer.
  • 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.
  • a reactor is any container(s) in which a chemical reaction occurs.
  • the new notation numbering scheme for the Periodic Table Groups are used as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).
  • Me is methyl
  • t-Bu and 1 Bu are tertiary butyl
  • iPr and 1 Pr are isopropyl
  • Cy is cyclohexyl
  • Ph is phenyl.
  • oligomer refers to compositions having 2-75 mer units
  • 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.
  • 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.
  • this invention relates to a multiple phase (preferably two or more phases) polymerization process operating below the melting point of the dry polymer, preferably between the melting point of the dry polymer and 8O 0 C below the melting point of the dry polymer, where the polymer is preferably not in solution in the polymerization media or effluent, that is modified by the addition of a fluorocarbon to the polymerization media or effluent.
  • the fluorocarbon is added in an amount such that the polymers produced precipitate out and remain solid particles in the reaction medium under the polymerization reaction conditions.
  • precipitates out is meant that upon addition of a fluorocarbon at least 0.1 weight % of the reaction medium is polymer present as solid particles, preferably at least 5 weight % of the reaction medium is present as solid particles, more preferably between 5 and 50 weight % is present as solid particles, more preferably between 10 and 45 weight %, more preferably between 15 and 40 weight %, more preferably between 20 and 35 weight %, more preferably between 25 and 30 weight % is present as solid particles.
  • the fluorocarbon may be added before, during and 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 and the FC may be the same or different as the FC added during the polymerization.
  • multiple phase is meant two or more phases, one of which comprises solid polymer particles.
  • melting point of the dry polymer or “Tm d” is meant the melting point of the neat polymer being produced, where the polymer has been stripped of residual solvents and monomers, before being subjected to the DSC procedure as follows: Differential scanning calorimetric (DSC) trace data is obtained using a TA Instruments model 2920 machine. Samples weighing approximately 7-10 mg are sealed in aluminum sample pans. The DSC data are recorded by first cooling the sample to -50 0 C and then gradually heating it to 200 °C at a rate of 10 °C/minute. The sample is kept at 200 0 C for 5 minutes before a second cooling- heating cycle is applied.
  • DSC Differential scanning calorimetric
  • the polymer is not in solution in the polymerization media or effluent
  • the polymer is present as a solid semi crystalline phase dispersed in a continuous liquid medium consisting of a solution of hydrocarbon/fluorocarbon, unreacted monomers, low molecular weight polymer being produced and catalyst components.
  • the process is operated at a temperature between the melting point of the dry polymer and 8O 0 C below the melting point of the dry polymer, preferably between 70 0 C below the dry melting point of the polymer and 50 0 C below the melting point of the dry polymer, preferably between 20 0 C below the dry melting point of the polymer and 6O 0 C below the melting point of the dry polymer, preferably between 25 0 C below the dry melting point of the polymer and 50 0 C below the melting point of the dry polymer.
  • the process is operated at a temperature between the melting point of the dry polymer and 2O 0 C below the melting point of the dry polymer, preferably between 5 0 C below the dry melting point of the polymer and 2O 0 C below the melting point of the dry polymer, preferably between 5 0 C below the dry melting point of the polymer and 15 0 C below the melting point of the dry polymer, preferably between 5 0 C below the dry melting point of the polymer and 10 0 C below the melting point of the dry polymer.
  • This invention relates to a process to produce polyethylene comprising contacting a homogeneous catalyst or catalyst system with 80 to 100 weight % ethylene and from 0 to 20 weight % of one or more C3 to C40 olefin comonomer(s), based upon the weight of the monomers present, in the presence of a fluorinated hydrocarbon and optionally a hydrocarbon solvent at a temperature below the reaction medium melting point and preferably above 65 0 C, preferably above 70 0 C, preferably above 75 0 C, preferably above 80 0 C.
  • the ethylene is present at 85 to 99.5 weight %, preferably at 90 to 99 weight %, more preferably at 95 to 98 weight %.
  • the comonomers if present are present at 0.5 to 15 weight %, preferably 1 to 10 weight %, more preferably 2 to 5 weight %.
  • the ethylene is present at 50 to 99.5 weight %, preferably at 70 to 99 weight %, more preferably at 80 to 95 weight %.
  • the comonomers, if present are present at 0.5 to 50 weight %, preferably 1 to 30 weight %, more preferably 5 to 20 weight %.
  • This invention also relates to a process to produce polypropylene comprising contacting a homogeneous catalyst or catalyst system with 50 to 100 weight % propylene and from 0 to 50 weight % of one or more of ethylene and C4 to C40 olefin comonomer(s), based upon the weight of the monomers present) in the presence of a fluorinated hydrocarbon and optionally a hydrocarbon solvent at a temperature below the reaction medium melting point and preferably above 65°C, preferably above 70 0 C, preferably above 75 0 C, preferably above 80 0 C.
  • the propylene is present at 60 to 99 weight %, preferably at 70 to 98 weight %, more preferably at 80 to 97 weight %, preferably at 90 to 97 weight %, more preferably at 93 to 96 weight %.
  • the comonomers are present at 1 to 40 weight %, preferably 2 to 30 weight %, more preferably 3 to 20 weight %, more preferably at 3 to 10 weight %, more preferably at 4 to 7 weight %.
  • the reaction medium melting point is determined by differential scanning calorimetery (DSC) of a sample of the polymer being produced that has been contacted with the fluorinated hydrocarbon(s) and any optional hydrocarbon solvent(s) as present in the polymerization medium for 12 hours at 50 0 C prior to measurement of the reaction medium melting point by DSC according to the following procedure: Differential scanning calorimetric (DSC) trace data is obtained using a TA Instruments model 2920 machine. Samples weighing approximately 7-10 mg are charged into hermetically sealed capsules (available from Perkin-Elmer as part number BOl 82901 capsule kit). The DSC data are recorded by first cooling the sample to -50 0 C and then gradually heating it to 200 °C at a rate of 10 °C/minute.
  • DSC differential scanning calorimetery
  • one or more fluorocarbons are added to a polymerization process in a polymerization reactor in an amount effective to induce polymer-solvent phase separation and to maintain the polymer produced as solid particles as compared to the exact same polymerization media or effluent without the fluorocarbon, preferably to maintain the polymer produced as solid particles in an amount of between 5 and 50 weight % ( based upon the weight of the polymerization medium), preferably between 10 and 40 weight %, preferably between 15 and 30 weight %.
  • 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 induce polymer- solvent phase separation and to maintain the polymer produced as solid particles, as compared to the exact same media or effluent without the fluorocarbon.
  • the polymerization process is one where the reaction medium comprises a hydrocarbon fluid (regardless of whether the fluid act as solvent or diluent) and one or more fluorocarbons are added to the polymerization reactor in an amount effective to induce polymer-solvent phase separation and to maintain the polymer produced as solid particles, as compared to the exact same media or effluent without the fluorocarbon.
  • the reaction medium comprises a hydrocarbon fluid (regardless of whether the fluid act as solvent or diluent) and one or more fluorocarbons are added to the polymerization reactor in an amount effective to induce polymer-solvent phase separation and to maintain the polymer produced as solid particles, as compared to the exact same media or effluent without the fluorocarbon.
  • Preferred hydrocarbon fluids 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, and other saturated C 6 to C 8 hydrocarbons.
  • the fluorocarbons are present in the polymerization media at 5 to 99 volume %, based upon the volume of the media, preferably the fluorocarbons are present at 10 to 90 volume %, preferably 20 to 70 more preferably at 20 to 60 volume %, more preferably 30 to 50 volume %.
  • polymerization media means the mixture of solvent/diluent and unreacted monomers.
  • the fluorocarbons are present in the polymerization effluent at 5 to 99 volume %, based upon the volume of the effluent, preferably the fluorocarbons are present at 10 to 80 volume %, preferably 20 to 50 volume %, more preferably at 25 to 50 volume %, more preferably 30 to 40 volume %.
  • polymerization effluent means the mixture of unreacted monomers, solvent/diluent, polymers produced and other additives introduced after polymerization reactor.
  • the polymerization processes of this invention are preferably conducted in the presence of a perfluorocarbon ("PFC” or “PFCs”) or a hydrofluorocarbon (“HFC” or “HFC's”), collectively referred to as “fluorinated hydrocarbons” or “fluorocarbons” (“FC” or “FCs”).
  • the fluorocarbon is inert to the polymerization reaction.
  • 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 FCs does not influence the polymerization reactions, in fact, it may do so to some extent, such as affecting activity rates.
  • the polymerization process is conducted without fluorocarbon present and the fluorocarbon is added to the polymerization effluent after the polymerization reaction has stopped, hi 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.
  • the polymerization process is conducted in the presence of fluorocarbon and additional fluorocarbon (which maybe 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 HyF 2 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.
  • hydrofluorocarbon and fluorocarbon do not include chlorofluorocarbons.
  • 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.
  • the hydrofluorocarbon is balanced or unbalanced in the number of fluorine atoms in the HFC used.
  • 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,
  • 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.
  • 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-365mfc having the chemical name 1,1,1,3,3- pentafluorobutane, R-318 having the chemical name octafluorocyclobutane, and HFC-43-lOmee having the chemical name 2,3-dihydrodecafluoropentane.
  • the fluorocarbon is not a perfluorinated C4 to ClO alkane. In another embodiment, the fluorocarbon is not a perfluorinated hydrocarbon. In another embodiment, the fluorocarbon is not perfluorodecalin, perfluoroheptane, perfluorohexane, perfluoromethylcyclohexane, perfluorooctane, perfluoro-l,3-dimethylcyclohexane, perfluorononane, fluorobenzene, or perfluorotoluene. In a particularly preferred embodiment, the fluorocarbon consists essentially of hydrofluorocarbons.
  • 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 %.
  • the fluorocarbon is present at more than 1 weight %, based upon the weight of the fluorocarbons, monomers and any hydrocrbon 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 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 %.
  • the fluorocarbon preferably the hydrofluorocarbon
  • the fluorocarbon 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 7volume %, 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 %.
  • 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 7volume %, 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 55volume %, preferably greater than 60 volume %, preferably greater than 65 volume %.
  • 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.
  • Mw weight average molecular weight
  • 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.
  • 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.
  • 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.
  • 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.
  • the fluorocarbons of the invention have normal boiling point in the range of from about -100 0 C up to the polymerization temperature, preferably up to about 7O 0 C, preferably up to about 85 to 115 0 C, preferably the normal boiling point of the fluorocarbons is in the range of from - 8O 0 C to about 9O 0 C, more preferably from about -6O 0 C to about 85 0 C, and most preferably from about -50 0 C to about 8O 0 C.
  • the fluorocarbons of the invention have normal boiling point greater than -5O 0 C, preferably greater than -50 0 C to less than -10 0 C.
  • the fluorocarbons of the invention have normal boiling point greater than -5 0 C, preferably greater than -5 0 C to less than -2O 0 C. In one embodiment, the fluorocarbons of the invention have normal boiling point greater than 1O 0 C, preferably greater than 1O 0 C to about 60 0 C. In another embodiment, the fluorocarbons of the invention have a liquid density @ 2O 0 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 1.20g/cc.
  • g/cc liquid density @ 2O 0 C
  • the fluorocarbons of the invention have a ⁇ H 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.
  • the fluorocarbons of the invention have any combination of two or more of the aforementioned Mw, normal boiling point, ⁇ H Vaporization, and liquid density values and ranges.
  • 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.
  • 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 0 C, preferably greater than -5O 0 C up to the polymerization temperature of the process, (such as up to 115 0 C), preferably less than 100 0 C, and more preferably less than 90 0 C, and most preferably less than 6O 0 C, and optionally a ⁇ H Vaporization in the range from 120kj/kg to 400 kj/kg.
  • the fluorocarbons are used in combination with one or more hydrocarbon solvents.
  • the hydrocarbon solvent is an aliphatic or aromatic hydrocarbon fluids.
  • 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, octane, isooctane, and other saturated C 6 to C 8 hydrocarbons.
  • Preferred hydrocarbon fluids also include desulphurized light virgin naphtha and alkanes (preferably Cl to C8 alkanes), such as propane, isobutane, mixed butanes, hexane, pentane, isopentane, cyclohexane, isooctane and octane.
  • desulphurized light virgin naphtha and alkanes such as propane, isobutane, mixed butanes, hexane, pentane, isopentane, cyclohexane, isooctane and octane.
  • mixtures of C3 to C20 paraffins and isoparaffins preferably paraffinic/isoparrifinic mixtures of C4, C5 and or C6 alkanes.
  • the fluorocarbon fluid is selected based upon its solubility or lack thereof in a particular polymer being produced. Preferred fluorocarbons have little to no solubility in the poly
  • 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%.
  • the fluorocarbon(s) or mixtures thereof, preferably, the FCs or mixtures thereof are selected such that the polymer melting temperature (Tm) is reduced (or depressed) by not more than 15 0 C by the presence of the fluorocarbon.
  • the depression of the polymer melting temperature ⁇ Tm 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 ⁇ Tm. Higher concentrations of dissolved materials in the polymer cause larger depressions in the polymer melting temperature (i.e. higher values of ⁇ Tm).
  • DSC differential scanning calorimetry
  • the ⁇ Tm 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 0 C.
  • the measured ⁇ Tm 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 I 0 C.
  • the fluorocarbon(s) or mixtures thereof are selected such that these are miscible to the hydrocarbon solvent and liquid monomers when a mixture is used.
  • 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.
  • the fluorocarbon(s) or mixtures thereof preferably, hydrofluorocarbon(s) or mixtures thereof, are selected such that they are immiscible to the hydrocarbon solvent and liquid monomers when a mixture is used.
  • 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.
  • the hydrocarbon, monomers and catalyst remain in one liquid phase, while the fluorocarbons stay in another liquid phase.
  • the liquid phase with hydrocarbon, monomers and catalyst forms droplets dispersed in the fluorocarbon phase.
  • the dispersed droplets may act as micro- reactors where polymerization takes place.
  • the fluorocarbon is selected such that upon significant polymerization, the polymer chains reach a crystallizable length and polymer phase separates from the reaction medium.
  • the polymerization then takes place at the interface of polymer particles.
  • simultaneous polymerization and crystallization may take place.
  • Successive polymerization and crystallization may occur for polymers with slow crystallization.
  • the fluorocarbon is selected such that the solvency of reaction medium decreases to an extent to induce polymer-solvent phase separation.
  • continuous is meant a system that operates (or is intended to operate) without interruption or cessation.
  • 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.
  • 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 solid particles in the polymerization media or polymerization effluent.
  • 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 250 0 C, preferably from 10 to 150 0 C, more preferably from 40 to 140, more preferably 50 to 12O 0 C and at pressures of 0.1 MPa or more, preferably 2 MPa or more.
  • 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.
  • a fluorocarbon is added to the polymerization reactor as a pure component or a mixture with other fluorocarbon and/or hydrocarbon. The amount of fluorocarbon is preferably sufficient so that the polymers produced remain in solid particle form when a mixture of fluorocarbon and hydrocarbon is used.
  • the 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.
  • 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.
  • the polymerization process is a single stage, steady state, polymerization conducted in a well-mixed continuous feed polymerization reactor.
  • 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.
  • substantially equal we intend that these amounts, polymer made per unit time, and polymer withdrawn per unit time, are in ratios of one to other, of from 0.9:1; or 0.95:1; or 0.97: 1 ; or 1 : 1.
  • the polymerization is accomplished in substantially single step or stage or in a single reactor, contrasted to multistage or multiple reactors (two or more).
  • the fluorocarbon is preferably injected into the first reactor feed, however the FC may also be injected into the reactor(s) directly.
  • the following procedure is carried out to obtain a copolymer, preferably comprising propylene and ethylene.
  • propylene monomer is introduced continuously together with solvent, 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.
  • a small amount of a "H"-branch inducing diene such as norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added.
  • the 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.
  • the polymerization rate is controlled by the rate of catalyst addition.
  • 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 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 further devolatilization in equipment such as a devolatilizing extruder or other devolatilizing equipment operated at reduced pressure.
  • 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 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.
  • 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.
  • comonomer such as ethylene
  • main monomer such as a propylene
  • any optional diene monomers present comonomer
  • the polymerization process is carried out with a pressure of ethylene of from 10 to 1000 psi (70 to 7000 kPa), most preferably from 40 to 800 psi (280 to 5440 kPa).
  • the polymerization is generally conducted at a temperature of from 25 to 250 0 C, preferably from 75 to 200 0 C, and most preferably from greater than 95 to 200 0 C.
  • a process for producing a propylene homopolymer or copolymer of propylene with at least one additional olefmic monomer selected from ethylene or C4 to C20 alpha-olefms 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.
  • 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.
  • 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, MMA03 A. MMAO-7, PMAO-IP (all available from Akzo Nobel).
  • the fluorocarbons may be introduced into the reactor as a mixture with one or more catalyst system components or a scavenger.
  • 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.
  • 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 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.
  • 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, MMA03A. MMAO-7, PMAO-IP (all available from Akzo Nobel).
  • 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.
  • 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.
  • 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 0.1 bar to 1600 bar (0.01-160 MPa), most preferably from 1.0 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.
  • the fluorocarbon may be introduced into one or all of the reactors, m 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.
  • the fluorocarbon 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 media or parts of reaction media.
  • 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, cyclohexane, isooctane, and octane.
  • 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, l'-bis(4- triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9- fluorenyl)hafiiium dimethyl, and or dimethylsilylbis(indenyl)hafitiium dimethyl; combined with dimethylaniliniumtetrakis-(perfluorophenyl) borate as an activator.
  • metallocene catalysts as described below, preferably, dimethylsilyl tetramethylcyclopentadienyl dodecylamide titanium dimethyl, rac- dimethylsilyl bis(2-methyl-4-pheny
  • An organoalurninurn 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 IsoparTM used as the solvent.
  • the reactors may be operated adiabatically or with a cooling loop.
  • 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
  • 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 barg (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 (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. %.
  • FC component(s) is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • the range of FCs 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 or b)
  • the extent of fluorination of the FCs is such that they form a single phase with the hydrocarbon solvent (preferably hexane) but are present in a controlled quantity to cause polymer precipitation in the polymerization reactors, but avoid precipitation in the reactor effluent preheater and first flash vessel at operating conditions.
  • 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.
  • the polymerization process preferably utilizes ametallocene catalyst, namely, 1, 1'- bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9- fluorenyl)hafhium dimethyl with dimethylaniliniumtetrakis(pentafluorophenyl) borate as an activator.
  • An organoaluminum compound namely, tri-n- octylaluminum, may be added as a scavenger to the monomer feedstreams prior to introduction into the polymerization process.
  • dimethylsilylbis(indenyl)hafhium dimethyl is used in combination with dimethylaniliniumtetrakis(pentafluorophenyl) borate.
  • 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.
  • 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.
  • 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.
  • LCST Critical Solution Temperature
  • 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. %.
  • a gear pump at the bottom of the flash vessel drives the polymer rich solution to a LIST devolatilizer.
  • An extruder is coupled to the end of the LIST devolatizer whereby the polymer material is transferred to a gear pump which pushes the polymer material through a screen pack. Then the polymer is cut into pellets and fed to a water bath.
  • a spin dryer dries the polymer pellets which have a final solvent content of less than about 0.5 wt.
  • FC component(s) Preferably a controlled volume of FC component(s) is mixed with the hydrocarbon solvent (hexanes) and monomers in the feed preparation section before injection into the reactors.
  • the range of FCs 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 7O 0 C, in addition the FCs, preferably have an anti-solvent effect, lower the critical solution phase cloud point curve making for more efficient separation in the liquid-liquid separator.
  • the FCs preferably separate with the hydrocarbon solvent in the polymer lean phase.
  • FCs could result in the operation of this critical solution separator at milder conditions of temperature and pressure; and/or b)
  • the extent of fluorination of the FCs is such that they form a single phase with the hexane solvent but are present in a controlled quantity to cause polymer precipitation in the polymerization reactors at operating conditions. Addition of fluorocarbon into the effluent makes the polymer-solvent phase separation at milder conditions (e.g., lower temperatures).
  • the process can be also simplified by replacing the LCST and associated heating unit with a conventional flash tank when sufficient amount of fluorocarbon is used.
  • EPDM polymers are produced in stirred flow reactors of either one or more stage, preferably in a one-stage reaction system in which a monomer mixture of ethylene, higher alpha-olefm and diene is fed into a reaction vessel along with a Ziegler-Natta catalyst, a cocatalyst and aromatic hydrocarbon solvent.
  • a monomer mixture of ethylene, higher alpha-olefm and diene is fed into a reaction vessel along with a Ziegler-Natta catalyst, a cocatalyst and aromatic hydrocarbon solvent.
  • the ethylene, higher alpha-olefin and non-conjugated diene are added to each reactor to maintain a relatively uniform composition of the terpolymer.
  • One such multi-stage method is disclosed in U.S. Pat. No. 3,629,212.
  • a terpolymer is prepared by (1) adding to a first reactor solvent, from about 50 to 90 percent by weight of the total ethylene charge, from about 30 to 100 percent by weight of the total higher alpha-olefin charge, from about 30 to 100 percent by weight of the total Ziegler-Natta catalyst charge, from about 30 to 100 percent by weight of the total organoaluminum cocatalyst charge and non-conjugated diene, (2) partially polymerizing a portion of the ethylene, higher alpha-olefin and diene in that first reactor to form a polymer cement (polymer dissolved in the solvent); (3) passing the reactor contents including the polymer cement from the first reactor to a second reactor connected in series with the first reactor; (4) adding ethylene to the second reactor along with an amount of non-conjugated diene such that the resultant polymerized weight percent diene content of the polymer from the first reactor is at least about 10 percent greater, on a relative basis, than the resultant polymerized
  • the resultant non- conjugated diene content in the polymer from the first reactor would be 6% and that from the second reactor 5%, the relative difference in diene content of the two polymers is at least 10%; in this example it is 20% greater.
  • the polymerization reaction of the discharged contents is terminated, and the terpolymer is collected and finished.
  • the reaction zones may be within a single reactor with horizontal baffles dividing the reactor into two or more distinct zones for polymerization.
  • separate feed inlets are provided for each reaction zone.
  • the same sequence of adding solvent, monomers, catalyst and cocatalyst is provided in each zone, as in the case of two separate reactors.
  • the process of the present invention can be performed by continuously feeding ethylene, C3 or higher alpha-olefin, non-conjugated diene, solvent, catalyst and cocatalyst into the first stirred reactor.
  • the polymer cement is fed directly from the first reactor to the second reactor.
  • Additional ethylene is fed continuously into the second reactor.
  • C3 or higher alpha-olefin is also fed continuously into the second reactor.
  • Some non-conjugated diene can also be added to the second or subsequent reactor in an amount such that the resulting polymerized weight percent diene content of the terpolymer from the first or preceding reactor is at least about 10 percent greater, on a relative basis, than the resulting polymerized weight percent diene content of the polymer from the second or following reactor.
  • the monomers are thus further polymerized in the second reactor.
  • Hydrogen, or other chain transfer agents may also be optionally fed to one or more reactors to control polymer molecular weight.
  • Any known solvent for the reaction mixture that is effective for the purpose can be used in conducting solution polymerizations in accordance with the present invention.
  • suitable solvents would be hydrocarbon solvents such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions of such solvents.
  • the preferred solvents are C 12 or lower, straight chain or branched chain, saturated hydrocarbons, C 5 to C 9 saturated alicyclic or aromatic hydrocarbons or C 2 to C 6 halogenated hydrocarbons. Most preferred are C 12 or lower, straight 11 chain or branched chain hydrocarbons, particularly hexane.
  • Nonlimiting illustrative examples of solvents are butane, pentane, hexane, heptane, cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methyl cyclohexane, isooctane, benzene, toluene, xylene, chloroform, chlorobenzenes, tetrachloroethylene, dichloroethane and trichloroethane.
  • a mix-free reactor system such as a plug flow reactor system
  • Suitable reactors are a continuous flow tubular or a stirred batch reactor.
  • a tubular reactor is well known and is designed to minimize mixing of the reactants in the direction of flow. As a result, reactant concentration will vary along the reactor length.
  • the reaction mixture in a continuous flow stirred tank reactor (CFSTR) is blended with the incoming feed to produce a solution of essentially uniform composition everywhere in the reactor. Consequently, the growing chains in a portion of the reaction mixture will have a variety of ages and thus a single CFSTR is not suitable for the process of this invention.
  • CFSTR continuous flow stirred tank reactor
  • 3 or more stirred tanks in series with all of the catalyst fed to the first reactor can approximate the performance of a tubular reactor.
  • a batch reactor is a suitable vessel, preferably equipped with adequate agitation, to which the catalyst, solvent, and monomer are added at the start of the polymerization. The charge of reactants is then left to polymerize for a time long enough to produce the desired product.
  • a tubular reactor is preferred to a batch reactor for carrying out the processes of this invention.
  • the desired polymer can be obtained if additional solvent and reactants (e.g., at least one of the ethylene, alpha-olefin and diene) are added either along the length of a tubular reactor or during the course of polymerization in a batch reactor. Operating in this fashion may be desirable in certain circumstances to control the polymerization rate or polymer composition.
  • the inlet temperature of the reactor feed could be about from -50° C. to 150° C. It is believed that the outlet temperature of the reaction mixture could be as high as about 200° C. The preferred maximum outlet temperature is about 70° C. The most preferred maximum is about 50° C. In the absence of reactor cooling, such as by a cooling jacket, to remove the heat of polymerization, it has been determined that the temperature of the reaction mixture will increase from reactor inlet to outlet by about 13° C. per weight percent of copolymer in the reaction mixture (weight of copolymer per weight of solvent).
  • the residence time of the reaction mixture in the mix-free reactor can vary over a wide range from as low as about 1 second to as high as 3600 seconds.
  • a preferred minimum is about 10 seconds.
  • the most preferred mim ' mum is about 15 seconds. It is believed that the maximum could be as high as about 3600 seconds.
  • a preferred maximum is about 1800 seconds.
  • the most preferred maximum is about 900 seconds.
  • Choice of reactor temperature is dependent upon the effect of temperature on catalyst deactivation rate. Temperatures should not exceed the point at which the concentration of catalyst in the second reactor is insufficient to make the desired polymer component in the desired amount. This temperature will be a function of the details of the catalyst system.
  • the first reactor temperature can vary between 0-110° C with 10-90°C preferred and 20-70 0 C most preferred.
  • Second reactor temperatures will vary from 40-140 0 C, with 50- 12O 0 C preferred and 60-110 0 C most preferred.
  • the reactors may be cooled by reactor jackets, cooling coils, auto refrigeration, pre-chilled feeds or combinations of these. Adiabatic reactors with pre-chilled feeds are preferred. This gives rise to a temperature difference between reactors which is helpful for controlling polymer molecular weight.
  • Residence time is the same or different in each reactor stage as set by reactor volumes and flow rates. Residence time is defined as the average length of time reactants spend within a process vessel. The total residence time, i.e.
  • the total time spent in all reactors is preferably 2-90 minutes and more preferably 540 minutes.
  • Polymer composition is controlled by the amount of monomers fed to each reactor of the train. In a two reactor series unreacted monomers from the first reactor flow into the second reactor and so the monomers added to the second reactor are just enough to adjust the composition of the feed to the desired level, taking into account the monomer carry over. Depending on reaction conditions in the first reactor (catalyst concentration, temperature, monomer feed rates, etc.) a monomer may be in excess in the reactor outlet relative to the amount required to make a certain composition in the second reactor. Since it is not economically feasible to remove a monomer from the reaction mixture, situations like this should be avoided by adjusting reaction conditions.
  • the polymer product can be recovered from solution at the completion of the polymerization by any of the techniques well known in the art such as steam stripping followed by extrusion drying or by devolatilizing extrusion.
  • Polymer molecular weight is controlled by reactor temperature, monomer concentration, and by the addition of chain transfer agents such as hydrogen. With metallocene catalysts, polymer molecular weight usually declines as reaction temperature increases. Adiabatic reactor operation in a two reactor series produces a higher temperature in the second reactor than the first making it easier to make the low molecular weight component in the second reactor. Molecular weight in the second reactor can be further reduced and MWD broadened by adding hydrogen to the second reactor.
  • Hydrogen can also be added to the first reactor but because unreacted hydrogen will carry over to the second reactor the molecular weight of both polymer components will be decreased in this situation and the effect of hydrogen on MWD will be much less.
  • a controlled volume of FC components is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • FCs 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 recovered hydrocarbon solvent, if any (typically hexanes) in the hexane purification tower, preferably the boiling point is in the range of from 0 to 7O 0 C, b) The extent of fluorination of the FCs is such that they form a single phase with the hexane solvent but are present in a controlled quantity to induce polymer precipitation in the polymerization reactors, but avoid precipitation in the reactor effluent preheater and first flash vessel at operating conditions.
  • ethylene polymers and copolymers are produced in a solution process at a pressure of 2.5 to 7.0, preferably 3.0 to 6.2 MPa, a temperature of 130 to 300 0 C, preferably 170 to 25O 0 C, in a hydrocarbon solvent, preferably an isoparaffin solvent, such as ISOPAR E TM (which is an isoparaffin solvent having a pour point of -63 0 C, a distillation range of 117-136 0 C, a specific gravity of 0.72, a viscosity of 0.85 cSt at 25 0 C, and less than 0.01 weight % aromatics, available from ExxonMobil Chemical Company, in Houston, Texas).
  • ISOPAR E TM which is an isoparaffin solvent having a pour point of -63 0 C, a distillation range of 117-136 0 C, a specific gravity of 0.72, a viscosity of 0.85 cSt at 25 0 C, and less than 0.01 weight % aromatics, available
  • monomer such as recycled or fresh ethylene compressed to 2.6 to 7.0 MPa
  • monomer such as recycled or fresh ethylene compressed to 2.6 to 7.0 MPa
  • the total stream is cooled to about -150 to 50 0 C, preferably to about 10-20 0 C, and transferred to a polymerization reactor(s) via a feed pump (the feed is preferably cooled to help maintain a reactor outlet temperature of about 220 to 240 0 C).
  • a feed pump the feed is preferably cooled to help maintain a reactor outlet temperature of about 220 to 240 0 C.
  • Single or multiple reactors in series may be used. If multiple reactors are used, it provides the opportunity for better control of heat removal and tailoring of product properties such as molecular weight, and molecular weight distribution and allows higher conversion for higher molecular weight products.
  • the system is preferably operated at low residence times, such as 3 to 20 minutes, preferably 5 to 12 minutes. Typically the system operates at 15 to 28% polymer in the solution, influenced principally by product melt index requirements and the impact on solution viscosity/mixing.
  • the melt solution effluent
  • the melt solution is typically heated and devolatilized in a first flash drum at 0.1 to 0.5 MPa.
  • the residual polymer with some solvent, fluorocarbon and comonomer may be further heated and transferred to a vacuum flash drum or vacuum falling strand evaporator for removal of residual volatiles operating at vacuum down to 20mm Hg.
  • the polymer melt from this vacuum vessel is finished in a static mixer or melt extruder to yield pellets.
  • ethylene polymers having densities up to 0.965 g/cc and ethylene octene copolymers below 0.940 g/cc density are produced by this process.
  • a controlled volume of FC components is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • FCs used is guided by a combination of: a) The boiling point of the FC is preferably higher than ethylene and thus are preferably co-condensed with the hydrocarbon solvent and unreacted comonomer (octene) in the overhead of the recycle wax separation stripper tower but preferably the boiling point of the FC is lower than octane/octene so that no residual FC remains in the finished polymer product pellets; and or b) The extent of fluorination of the FCs is such that they form a single phase with the isooctane solvent but are present in a controlled quantity to induce polymer precipitation in the polymerization reactors but not in the first flash vessel at operating conditions.
  • ethylene polymers and copolymers are produced in a solution process at a pressure of 4.0 to 7.0, preferably 4.5 to 6.3 MPa, a temperature of 120 to 300 0 C, preferably 125 to 235 0 C, in a hydrocarbon solvent, preferably an isoparaffin solvent, such as ISOPAR E TM (which is an isoparaffin solvent having a pour point of -63°C, a distillation range of 117-136°C, a specific gravity of 0.72, a viscosity of 0.85 cSt at 25 0 C, and less than 0.01 weight % aromatics, available from ExxonMobil Chemical Company, in Houston, Texas), hi a particularly preferred embodiment, monomer (such as recycled or fresh ethylene compressed to 4.6 to 7.0 MPa) is mixed with fresh comonomer, fresh solvent and any recycle solvent-comonomer blend.
  • ISOPAR E TM which is an isoparaffin solvent having a pour point of -63°C, a distillation range
  • the total stream is cooled to about -150 to 50 0 C, preferably to about 10-20 0 C, and transferred to a polymerization reactor(s) via a feed pump.
  • These reactors are of a loop design fitted with one or two heat exchangers cooled by tempered water to avoid crystallization deposition on the exchanger surface.
  • a single loop reactor or 2 loop reactors arranged either in series or parallel may be used. If multiple reactors are used, it provides the opportunity for better control of heat removal and tailoring of product properties such as molecular weight, and molecular weight distribution.
  • Fresh monomer, comonomer additional catalyst or another catalyst may be injected in the second reactor when in series operation. In parallel operation the conditions and even catalyst types may differ between the two reactors.
  • Both reactor effluent solutions are combined before flashing and polymer recovery to allow efficient mixing of differing polymer structures.
  • the system is preferably operated at low residence times, such as 3 to 20 minutes, preferably 5 to 12 minutes. Typically the system operates at 15 to 28% polymer in the solution, influenced principally by product melt index requirements and the impact on solution viscosity/mixing.
  • the melt solution is typically heated and devolatilized in a first flash drum at 0.1 to 0.5 MPa.
  • the residual polymer with some solvent, fluorocarbon and comonomer may be further heated and transferred to a vacuum flash drum or vacuum falling strand evaporator for removal of residual volatiles operating at vacuum down to 20mm Hg.
  • the polymer melt from this vacuum vessel is finished in a static mixer or melt extruder to yield pellets.
  • a controlled volume of FC components is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • the range of FCs used is guided by a combination of: a) the boiling point of the FC is preferably is higher than ethylene such that the FCs are co-condensed with the hydrocarbon solvent and unreacted comonomer (octene) in the overhead of the recycle wax separation stripper tower but lower than octane/octene so that no residual FC remains in the finished polymer product pellets; and/or b)
  • the extent of fluorination of the FCs is such that they form a single phase with the isooctane solvent but are present in a controlled quantity to cause polymer precipitation in the polymerization reactors but not in the first flash vessel at operating conditions.
  • ethylene polymers having densities up to 0.965 g/cc and ethylene octene copolymers below 0.940 g/cc down to 0.865cc/g density are produced by this process.
  • ethylene with one or more olefins (C3 to C20) are mixed with a paraffinic solvent such as Isopar E and cooled to -40 to O 0 C.
  • Catalyst components are injected as solutions either directly into the reactor or just before the reaction zone.
  • the polymerization is carried out in one or more reactors in series operating at pressures up to lOOMPa and temperatures in the range 40 to 14O 0 C.
  • reactors may be continuous stirred tanks or loop type with the ability for heat removal through the reactor wall or via a heat exchanger in the reactor loop.
  • the polymer solution is continuously removed, heated to 150- 24O 0 C before entering a low pressure flash vessel at 0.1 to 0.5MPa.
  • the volatile materials are condensed and recycled.
  • the polymer cement is transferred to a vacuum flash system for removal of residual solvent, monomers and waxes and the resulting polymer melt is finished in a devolatilizing extruder.
  • a catalyst killer such as water, a low boiling alcohol or carboxylic acid is injected at levels sufficient to deactivate all remaim ' ng catalytic activity.
  • polymerization of ethylene and an alpha olefin such as octene- 1 is carried out in a single agitated liquid filled vessel under adiabatic conditions at a temperature between 150 and 250 0 C, and a pressure of 450 and 1400psi (3.1 to 9.7 MPa) with a hydrocarbon solvent such as mixed hexane or desulphurized light virgin naphtha present at a residence time of 20 minutes or less, preferably 10 minutes or less.
  • This reactor effluent is heated and depressurized to 0.1 to 0.5 MPa in a flash vessel where unreacted ethylene and most solvent and comonomer exits as vapor for recovery and recycle.
  • a solution of stabilizers in isopropanol is injected into the polymer melt to deactivate the catalyst.
  • This mixture is then pumped to either a devolatilizing twin screw extruder operating at 20mm Hg or passes a falling strand vacuum evaporator before being finished in a melt extruder. Both finishing methods remove residual comonomer, solvent and some waxy product. Solvent, unreacted monomers and waxy side products are condensed and the liquid is water washed to remove isopropanol and stripped to separate waxy materials.
  • the hydrocarbons are dried and purified over fixed bed adsorbents before recycling to the feed preparation drum.
  • This process preferably is used to produce homopolymers of ethylene and copolymers of ethylene and butene, pentene, hexene, heptene and or octene, preferably butene, hexene and or octene, having densities from 0.880 to 0.965g/cc, preferably from 0.900 to 0.965 g/cc and melt indices of 0.5 to lOOdg/min (ASTM 1238, condition E).
  • a controlled volume of FC components is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • FCs used is guided by a combination of: a) The boiling point of the FC is preferably higher than ethylene (preferably in the range of from 0 to 7O 0 C) so that the FC and the monomers co- condense and recycle with the hydrocarbon solvent (hexanes); and/or b) The extent of fluorination of the FCs is such that they form a single phase with the hexane solvent but are present in a controlled quantity to cause polymer precipitation in the polymerization reactors, but not in the reactor effluent preheater and first flash vessel at operating conditions.
  • polymerization is carried out in a single or in multiple reactors at a temperature up to 300 0 C and pressures up to 2000 psi (13.6 MPa) using a hydrocarbon solvent such as cyclohexane where the feed stream does not have to be refrigerated, the residence times are 10 minutes or less, preferably 5 minutes or less, more preferably 2 minutes or less to produce ethylene homopolymers and copolymers of ethylene and butene and or hexene.
  • the reactors may be stirred tank, tubular or a combination thereof. Generally the ethylene is mixed with solvent and comonomer, pressurized and fed into the reactor along with the catalyst.
  • a catalyst deactivator may be added to the solution stream to deactivate the catalyst.
  • the deactivator and or deactivated catalyst may then be removed down stream ( by alumina beds, for example). Then the molten polymer stream is depressurized where solvent and monomer are flashed off. Steam stripping of the final polymer melt may be carried out to remove waxes and any residual solvent and comonomers before finishing with a melt extruder/pelletizer.
  • multiple reactors particularly a stirred tank in series with a tube, are used.
  • a controlled volume of FC components is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • FCs used is guided by a combination of: a) The boiling point of the FC is preferably higher than ethylene (preferably in the range of from 0 to 7O 0 C) so that the FC and the monomers co- condense and recycle with the hydrocarbon solvent (cyclohexane); and/or b) The extent of fluorination of the FCs is such that they form a single phase with the cyclohexane solvent but are present in a controlled quantity to cause polymer precipitation in the polymerization reactors, but not in the reactor effluent preheater or first flash vessel at operating conditions.
  • two continuous stirred tanks in series operating at pressures up to 180 MPa with a light hydrocarbon paraffinic solvent such as propane, butane, pentane or hexane may be used with the possibility to inject additional monomer, comonomer and catalyst into the second reactor.
  • the reactor effluent is heated, flashed first at low pressures, below 0.5MPa and then at vacuum before finishing in an extruder, hi such an embodiment, preferably a controlled volume of FC components is mixed with the hydrocarbon solvent and monomers in the feed preparation section before injection into the reactors.
  • FCs used is guided by a combination of: a) The boiling point of the FC is higher than ethylene so the FCs are not lost with any process degassing and the FCs should boil with the process solvent (i.e. have a boiling point lower than the solvent) to minimize loss into the polymer product; and or b) The extent of fluorination of the FCs is such that they form a single phase with the isooctane solvent but are present in a controlled quantity to cause polymer precipitation in the polymerization reactors but not in the first flash vessel at operating conditions.
  • any of the polymerization process described herein are a continuous process. hi any of the embodiments described herein the materials stripped or flashed off may be passed through activated carbon to remove all or part of the FCs.
  • AU polymerization catalysts including conventional-type transition metal catalysts are suitable for use in the polymerization process of the invention.
  • the following is a non-limiting discussion of the various polymerization catalysts useful in the process of the invention.
  • Conventional-type transition metal catalysts are those traditional Ziegler- Natta catalysts and Phillips-type chromium catalyst well known in the art. Examples of conventional-type transition metal catalysts are discussed in U.S. Patent Nos. 4,115,639, 4,077,9044,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741 all of which are herein fully incorporated by reference.
  • the conventional-type transition metal catalyst compounds that may be used in the present invention include transition metal compounds from Groups 3 to 10, preferably 4 to 6 of the Periodic Table of Elements.
  • These conventional-type transition metal catalysts may be represented by the formula: MR x (I) where M is a metal from Groups 3 to 10, preferably Group 4, more preferably titanium; R is a halogen or a hydrocarbyloxy group; and x is the valence of the metal M, preferably x is 1, 2 ,3 or 4, more preferably x is 4.
  • R include alkoxy, phenoxy, bromide, chloride and fluoride.
  • Non- limiting examples of conventional-type transition metal catalysts where M is titanium include TiCl 3 , TiCl 4 , TiBr 4 , Ti(OC 2 H 5 ) 3 Cl, Ti(OC 2 H 5 )Cl 3 , Ti(OC 4 H 9 ) 3 Cl, Ti(OC 3 H 7 ) 2 Cl 2 , Ti(OC 2 Hs) 2 Br 2 , TiCl 3 .1/3AlCl 3 and Ti(OC 12 H 25 )Cl 3 .
  • Conventional-type transition metal catalyst compounds based on magnesium/titanium electron-donor complexes that are useful in the invention are described in, for example, U.S. Patent Nos. 4,302,565 and 4,302,566, which are herein fully incorporate by reference.
  • the MgTiCl 6 (ethyl acetate) 4 derivative is particularly preferred.
  • British Patent Application 2,105,355, herein incorporated by reference, describes various conventional-type vanadium catalyst compounds.
  • Non-limiting examples of conventional-type vanadium catalyst compounds include vanadyl trihalide, alkoxy halides and alkoxides such as VOCl 3 , VOCl 2 (OBu) where Bu is butyl and VO(OC 2 H 5 ) 3 ; vanadium tetra-halide and vanadium alkoxy halides such as VCl 4 and VCl 3 (OBu); vanadium and vanadyl acetyl acetonates and chloroacetyl acetonates such as V(AcAc) 3 and VOCl 2 (AcAc) where (AcAc) is an acetyl acetonate.
  • the preferred conventional-type vanadium catalyst compounds are VOCl 3 , VCl 4 and VOCl 2 -OR where R is a hydrocarbon radical, preferably a C 1 to C 10 aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates.
  • R is a hydrocarbon radical, preferably a C 1 to C 10 aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acet
  • Conventional-type chromium catalyst compounds often referred to as Phillips-type catalysts, suitable for use in the present invention include CrO 3 , chromocene, silyl chromate, chromyl chloride (CrOaCl 2 ), chromium-2-ethyl- hexanoate, chromium acetylacetonate (Cr(AcAc) 3 ), and the like.
  • Non-limiting examples are disclosed in U.S. Patent Nos. 2,285,721, 3,242,099 and 3,231,550, which are herein fully incorporated by reference.
  • Still other conventional-type transition metal catalyst compounds and catalyst systems suitable for use in the present invention are disclosed in U.S. Patent Nos.
  • the conventional-type transition metal catalysts of the invention may also have the general formula: M ⁇ M 11 X 21 Y u E (D) where M 1 is Mg, Mn and/or Ca; t is a number from 0.5 to 2; M" is a transition metal such as Ti, V and/or Zr; X is a halogen, preferably Cl, Br or I; Y may be the same or different and is halogen, alone or in combination with oxygen, -NR 2 , -OR, -SR, -COOR, or -OSOOR, where R is a hydrocarbyl radical, in particular an alkyl, aryl, cycloalkyl or arylalkyl radical, acetylacetonate anion in an amount that satisfies the
  • Non-limiting examples of complexes satisfying the above formula include: MgTiCl 5 ⁇ CH 3 COOC 2 H 55 Mg 3 Ti 2 Cl 12 7CH 3 COOC 2 H 5 , MgTiCl 5 ⁇ C 2 H 5 OH, MgTiCl 5 ' 100CH 3 OH, MgTiClstetrahydrofuran, MgTi 2 Cl 12 7C 6 H 5 CN, Mg 3 Ti 2 Cl 12 -OC 6 H 5 COOC 2 H 5 , MgTiCl 6 2CH 3 COOC 2 H 5 , MgTiCl 6 OC 5 H 5 N, MnTiCl 5 4C 2 H 5 OH, MgTiCl 5 (OCH 3 )-2CH 3 COOC 2 H 5 , MgTiCl 5 N(C 6 H 5 ) 2 -3CH 3 COOC 2 H 5 , MgTiBr 2 Cl 4 ⁇ (C 2 Hs) 2 O, Mg 3 V 2 Cl 12 7CH 3 -
  • catalysts may include cationic catalysts such as AlCl 3 , and other cobalt and iron catalysts well known in the art.
  • these conventional-type transition metal catalyst compounds (excluding some conventional-type chromium catalyst compounds) are activated with one or more of the conventional-type cocatalysts described below.
  • the catalyst system not comprise titanium tetrachloride, particularly not the combination OfTiCl 4 and aluminum alkyl (such as triethylaluminum), particularly when the FC is a perfluorocarbon.
  • the catalyst is titanium tetrachloride, particularly the combination OfTiCl 4 and aluminum alkyl (such as triethylaluminum)
  • the FC is preferably a hydrofluorocarbon.
  • the catalyst is not a free radical initiator, such as a peroxide.
  • Conventional-type cocatalyst compounds for the above conventional-type transition metal catalyst compounds may be represented by the formula: M 3 M 4 v X 2 c R 3 b-c (M) wherein M 3 is a metal from Group 1, 2, 12 and 13 of the Periodic Table of Elements; M 4 is a metal of Group IA of the Periodic Table of Elements; v is a number from 0 to 1; each X is any halogen; c is a number from 0 to 3; each R is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and wherein b minus c is at least 1.
  • M 3 R ⁇ (IV) M 3 R ⁇ (IV) where M 3 is a Group 1, 2, 12 or 13 metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3 depending upon the valency of M 3 which valency in turn normally depends upon the particular Group to which M 3 belongs; and each R 3 may be any monovalent hydrocarbon radical.
  • M 3 is a Group 1, 2, 12 or 13 metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium
  • k equals 1, 2 or 3 depending upon the valency of M 3 which valency in turn normally depends upon the particular Group to which M 3 belongs
  • each R 3 may be any monovalent hydrocarbon radical.
  • Non-limiting examples of conventional-type organometallic cocatalyst compounds of Groups 1, 2, 12 and 13 useful with the conventional-type catalyst compounds described above include methyllithiurn, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc, tri-n- butylaluminum, diisobutyl ethylboron, diethylcadmium, di-n-butylzinc and tri-n- amylboron, and, in particular, the aluminum alkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum, and tri-isobutylaluminum.
  • Non-limiting examples of such conventional-type cocatalyst compounds include di-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethylberyllium chloride, ethylcalcium bromide, di- isobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminum hydride and bromocadmium hydride.
  • polymerization catalysts useful in the invention include one or more bulky ligand metallocene compounds (also referred to herein as metallocenes).
  • Typical bulky ligand metallocene compounds are generally described as containing one or more bulky ligand(s) and one or more leaving group(s) bonded to at least one metal atom.
  • the bulky ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof.
  • the ring(s) or ring system(s) are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements; preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof.
  • the ring(s) or ring system(s) are composed of carbon atoms such as, but not limited to, those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand.
  • the metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements.
  • the metal is a transition metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4.
  • Exemplary of these bulky ligand metallocene-type catalyst compounds and catalyst systems are described in for example, U.S. Patent Nos.
  • EP-A-O 591 756, EP-A-O 520 732, EP-A- 0 420 436, EP-Bl 0 485 822, EP-Bl 0 485 823, EP-A2-0 743 324 and EP-Bl 0 518 092 and PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO 98/01455, WO 98/06759 and WO 98/011144 are all herein fully incorporated by reference for purposes of describing typical bulky ligand metallocene-type catalyst compounds and catalyst systems.
  • the catalyst composition of the invention includes one or more bulky ligand metallocene catalyst compounds represented by the formula: L A L B MQ n (V) where M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is a Group 4 transition metal, even more preferably M is zirconium, hafnium or titanium.
  • M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is a Group 4 transition metal, even more preferably M is zirconium, hafnium or titanium.
  • the bulky ligands, L A and L B are open, acyclic or fused ring(s) or ring system(s) and are any ancillary ligand system, including unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands.
  • Non- limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands.
  • L A and L B may be any other ligand structure capable of ⁇ -bonding to M.
  • the atomic molecular weight (MW) of L A or L B exceeds 60 a.m.u., preferably greater than 65 a.m.u.
  • L ⁇ and L B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a hetero-cyclopentadienyl ancillary ligand.
  • L A and L B bulky ligands include but are not limited to bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
  • each L A and L B may be the same or different type of bulky ligand that is bonded to M.
  • Formula HI only one of either L A or L B is present.
  • each L A and L B may be unsubstituted or substituted with a combination of substituent groups R.
  • Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof.
  • substituent groups R have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like.
  • alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like.
  • hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)- silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulf
  • Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to olefmically unsaturated substituents including vinyl- terminated ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof.
  • a substituent group R group such as 1-butanyl may form a carbon sigma bond to the metal M.
  • Other ligands may be bonded to the metal M, such as at least one leaving group Q.
  • Q is a monoanionic labile ligand having a sigma- bond to M.
  • the value for n is 0, 1 or 2 such that Formula V above represents a neutral bulky ligand metallocene catalyst compound.
  • Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof.
  • weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof.
  • two or more Q's form a part of a fused ring or ring system.
  • Q ligands include those substituents for R as described above and including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N- methylanilide), dimethylamide, dimethylphosphide radicals and the like.
  • the catalyst composition of the invention may include one or more bulky ligand metallocene catalyst compounds where L A and L B of Formula V are bridged to each other by at least one bridging group, A, as represented by: L A AL B MQ n (VI) wherein L A , L B , M, Q and n are as defined above.
  • bridging group A include bridging groups containing at least one Group 13 to 16 atom, often referred to as a divalent moiety such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or a combination thereof.
  • bridging group A contains a carbon, silicon or germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom.
  • the bridging group A may also contain substituent groups R as defined above including halogens and iron.
  • Non- limiting examples of bridging group A maybe represented by R' 2 C, R' 2 Si, R' 2 Si R' 2 Si, R' 2 Ge, RT, where R' is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen or two or more R' may be joined to form a ring or ring system.
  • the bridged, bulky ligand metallocene catalyst compounds of Formula VI have two or more bridging groups A (EP 664 301 Bl).
  • the bulky ligand metallocene catalyst compounds are those where the R substituents on the bulky ligands L A and L B of Formulas V and VI are substituted with the same or different number of substituents on each of the bulky ligands.
  • the bulky ligands L A and L B of Formulas V and VI are different from each other.
  • Other bulky ligand metallocene catalyst compounds and catalyst systems useful in the invention may include those described in U.S. Patent Nos.
  • the catalyst compositions of the invention may include bridged heteroatom, mono-bulky ligand metallocene compounds.
  • These types of catalysts and catalyst systems are described in, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/ 04257, WO 94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European publication EP-A-O 420436, all of which are herein fully incorporated by reference.
  • the catalyst composition of the invention includes one or more bulky ligand metallocene catalyst compounds represented by Formula VII: L 0 AJMQ n (VD) where M is a Group 3 to 16 metal atom or a metal selected from the Group of actinides and lanthanides of the Periodic Table of Elements, preferably M is a Group 4 to 12 transition metal, and more preferably M is a Group 4, 5 or 6 transition metal, and most preferably M is a Group 4 transition metal in any oxidation state, especially titanium; L c is a substituted or unsubstituted bulky ligand bonded to M; J is bonded to M; A is bonded to J and L c ; J is a heteroatom ancillary ligand; and A is a bridging group; Q is a univalent anionic ligand; and n is the integer 0,1 or 2.
  • M is a Group 3 to 16 metal atom or a metal selected from the Group of actinides and lanthanides of the Periodic Table
  • L c , A and J form a fused ring system.
  • L c of Formula V is as defined above for L A , A, M and Q of Formula VII are as defined above in Formula V.
  • J is a heteroatom containing ligand in which J is an element with a coordination number of three from Group 15 or an element with a coordination number of two from Group 16 of the Periodic Table of Elements.
  • J contains a nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being most preferred.
  • the FC preferably is a hydrofluorocarbon.
  • the FC is not a perfluorocarbon.
  • the bulky ligand metallocene catalyst compounds are heterocyclic ligand complexes where the bulky ligands, the ring(s) or ring system(s), include one or more heteroatoms or a combination thereof.
  • heteroatoms include a Group 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examples of these bulky ligand metallocene catalyst compounds are described in WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-Al-O 874 005 and U.S. Patent No.
  • the bulky ligand metallocene catalyst compounds are those complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. Application Serial No. 09/103,620 filed June 23, 1998, which is herein incorporated by reference.
  • the bulky ligand metallocene catalyst compounds are those described in PCT publications WO 99/01481 and WO 98/42664, which are fully incorporated herein by reference.
  • the bulky ligand metallocene catalyst compound is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bonded ligand, and one or more heteroallyl moieties, such as those described in U.S. Patent Nos. 5,527,752 and 5,747,406 and EP-Bl-O 735 057, all of which are herein fully incorporated by reference.
  • the catalyst composition of the invention includes one or more bulky ligand metallocene catalyst compounds is represented by Formula vm: L 0 MQ 2 (YZ)X n (Vm) where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal; L D is a bulky ligand that is bonded to M; each Q is independently bonded to M and Q 2 (YZ) forms a ligand, preferably a unicharged polydentate ligand; or Q is a univalent anionic ligand also bonded to M; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; n is 1 or 2.
  • M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal
  • L D is a bulky ligand that is bonded to M
  • each Q is independently
  • Q is as defined above for Formula V, preferably Q is selected from the group consisting of -O-, -NR-, -CR2- and -S-; Y is either C or S; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SiR3, -PR2, -H, and substituted or unsubstituted aryl groups, with the proviso that when Q is -NR- then Z is selected from one of the group consisting of -OR, -NR2, -SR, -SiR3, -PR2 and -H; R is selected from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is an integer from 1 to 4, preferably 1 or 2; X is
  • Still other useful catalysts include those multinuclear metallocene catalysts as described in WO 99/20665 and 6,010,794, and transition metal metaaracyle structures described in EP 0 969 101 A2, which are herein incorporated herein by reference.
  • Other metallocene catalysts include those described in EP 0 950 667 Al, double cross-linked metallocene catalysts (EP 0 970074 Al), tethered metallocenes (EP 970 963 A2) and those sulfonyl catalysts described in U.S. Patent No. 6,008,394, which are incorporated herein by reference.
  • the bulky ligand metallocene catalysts include their structural or optical or enantiomeric isomers (meso and racemic isomers, for example see U.S. Patent No. 5,852,143, incorporated herein by reference) and mixtures thereof.
  • the bulky ligand type metallocene-type catalyst compound is a complex of a transition metal, a substituted or unsubstituted pi- bonded ligand, and one or more heteroallyl moieties, such as those described in U.S. Patent No. 5,527,752 and 5,747,406 and EP-Bl-O 735 057, all of which are herein fully incorporated by reference.
  • the catalyst compositions of the invention may include one or more complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. Patent No. 6,103,657, which is herein incorporated by reference.
  • these catalyst compounds are represented by the formula: ((Z)XA t (YJ)) q MQ n (DC) where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, bivalent, or trivalent anion; X and Y are bonded to M; one or more of X and Y are heteroatoms, preferably both X and Y are heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Z comprises 1 to 50 non- hydrogen atoms, preferably 1 to 50 carbon atoms, preferably Z is a cyclic group containing 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a bridging group joined to at least one of
  • the bulky ligand metallocene- type catalyst compounds are those nitrogen containing heterocyclic ligand complexes, also known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in WO 96/33202, WO 99/01481 and WO 98/42664 and U.S. Patent No. 5,637,660, which are herein all incorporated by reference.
  • the catalyst compounds include complexes of Ni and Pd described in the articles Johnson, et al., "New Pd(H)- and Ni(H)- Based Catalysts for Polymerization of Ethylene and a-Olefms", J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al., "Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts", J. Am. Chem. Soc, 1996, 118, 267-268, and WO 96/23010 published August 1, 1996, WO 99/02472, U.S. Patent Nos.
  • bulky ligand metallocene-type catalysts useful herein are those Group 5 and 6 metal imido complexes described in EP-A2-0 816 384 and U.S. Patent No. 5,851,945, which is incorporated herein by reference.
  • bulky ligand metallocene-type catalysts useful herein include bridged bis(arylamido) Group 4 compounds described by D.H. McConville, et al., in Organometallics 1195, 14, 5478-5480, which is herein incorporated by reference.
  • Other bulky ligand metallocene-type catalysts useful herein are described as bis(hydroxy aromatic nitrogen ligands) in U.S. Patent No. 5,852, 146, which is incorporated herein by reference.
  • metallocene-type catalysts containing one or more Group 15 atoms useful herein include those described in WO 98/46651, which is herein incorporated herein by reference. Still another metallocene-type bulky ligand metallocene-type catalysts useful herein include those multinuclear bulky ligand metallocene-type catalysts as described in WO 99/20665, which is incorporated herein by reference. In addition, useful Group 6 bulky ligand metallocene catalyst systems are described in U.S. Patent No. 5,942,462, which is incorporated herein by reference.
  • the bulky ligands of the metallocene-type catalyst compounds of the invention described above maybe asymmetrically substituted in terms of additional substituents or types of substituents, and/or unbalanced in terms of the number of additional substituents on the bulky ligands or the bulky ligands themselves are different.
  • the bulky ligand metallocene-type catalysts of the invention include their structural or optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof.
  • the bulky ligand metallocene-type compounds useful in the invention may be chiral and/or a bridged bulky ligand metallocene-type catalyst compound.
  • the above described bulky ligand metallocene-type catalyst compounds can be combined with one or more of the conventional-type transition metal catalysts compounds with one or more co- catalysts or activators or activation methods described above.
  • one or more bulky ligand metallocene-type catalyst compounds or catalyst systems may be used in combination with one or more conventional-type catalyst compounds or catalyst systems.
  • Mixed catalysts and catalyst systems are described in U.S. Patent Nos.
  • activator is defined to be any compound which can activate any one of the catalyst compounds described herein by converting the neutral catalyst compound to a catalytically active catalyst cation compound.
  • Non-limiting activators include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • alumoxane activators are utilized as an activator in the catalyst composition of the invention.
  • Alumoxanes are generally oligomeric compounds containing -Al(R)-O- subunits, where R is an alkyl group.
  • Non- limiting examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound.
  • MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum.
  • MMAO' s are generally more soluble in aliphatic solvents and more stable during storage.
  • methods for preparing alumoxane and modified alumoxanes are described in U.S. Patent No.
  • alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3 A (commercially available from Akzo Chemicals, Lie. under the trade name Modified Methylalumoxane type 3 A, covered under patent number US 5,041,584).
  • MMAO modified methyl alumoxane
  • Aluminum Alkyl or organoaluminum compounds which may be utilized as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.
  • neutral or ionic such as tri (n-butyl) ammom ' um tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Non-limiting examples of neutral stoichiometric activators include tri- substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups.
  • the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.
  • substituted alkyl refers to an alkyl as described in which one or more hydrogen atoms of the alkyl is replaced by another group such as a halogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, and combinations thereof. Examples of substituted alkyls include, for example, benzyl, trifluoromethyl and the like.
  • Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European publications EP-A-O 570 982, EP-A-O 520 732, EP-A-O 495 375, EP-Bl-O 500 944, EP-A-O 277 003 and EP-A-O 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No.
  • the stoichiometric activators include a cation and an anion component, and may be represented by the following formula: (L-H) d + -(A d -) (X) wherein: L is an neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A d ⁇ is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.
  • the cation component, (L-H)a + may include Bronsted acids such as protons or protonated Lewis bases or reducible Catalysts capable of protonating or abstracting a moiety, such as an akyl or aryl, from the bulky ligand metallocene or Group 15 containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation (L-H) d + maybe a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamme, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N 5 N- dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane,
  • the activating cation (L-H)/ may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably (L-H) d + is triphenyl carbonium.
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • suitable A d' also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.
  • the ionic stoichiometric activator (L-H) d + *(A d ⁇ ) is N 9 N- dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.
  • an activation method using ionizing ionic compounds not containing an active proton but capable of producing a bulky ligand metallocene catalyst cation and their non-coordinating anion are also contemplated, and are described in EP-A- 0426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
  • activators include those described in PCT publication WO 98/07515 such as tris (2, 2', 2"- nonafluorobiphenyl) fluoroaluminate, which publication is fully incorporated herein by reference.
  • Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-Bl 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410 all of which are herein fully incorporated by reference.
  • WO 98/09996 describes activating bulky ligand metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates.
  • WO 98/30602 and WO 98/30603 describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate)*4THF as an activator for a bulky ligand metallocene catalyst compound.
  • WO 99/18135, incorporated herein by reference describes the use of organo-boron-aluminum activators.
  • EP-Bl-O 781 299 describes using a silylium salt in combination with a non-coordinating compatible anion.
  • methods of activation such as using radiation (see EP- Bl-0 615 981 herein incorporated by reference), electro-chemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral bulky ligand metallocene catalyst compound or precursor to a bulky ligand metallocene cation capable of polymerizing olefins.
  • Other activators or methods for activating a bulky ligand metallocene catalyst compound are described in for example, U.S. Patent Nos.
  • Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula: wherein: OX e+ is a cationic oxidizing agent having a charge of e+; e is an integer from 1 to 3; and A " , and d are as previously defined above.
  • Non-limiting examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl- substituted ferrocenium, Ag + , or Pb +2 .
  • Preferred embodiments of A " are those anions previously defined with respect to the Bronsted acid containing activators, especially tetrakis(pentafluorophenyl)borate. It within the scope of this invention that catalyst compounds can be combined one or more activators or activation methods described above. For example, a combination of activators have been described in U.S. Patent Nos. 5,153,157 and 5,453,410, European publication EP-Bl 0 573 120, and PCT publications WO 94/07928 and WO 95/14044.
  • a preferred catalyst compound for use in this invention is dimethylsilyl t- butyl-amido tetramethylcyclopentadienyl titanium dichloride, preferably activated with a noncoordinating anion such as dimethylaniliniumtetrakis (pentafluorophenyl) borate.
  • the processes of this invention are used to polymerize any unsaturated monomer or monomers.
  • Preferred monomers include C 2 to C 1 Oo olefins, preferably C 2 to C 6 o olefins, preferably C 2 to C 40 olefins preferably C 2 to C 20 olefins, preferably C 2 to C 12 olefins.
  • preferred monomers include linear, branched or cyclic alpha-olefins, preferably C 2 to C 10O alpha-olefins, preferably C 2 to C 60 alpha-olefins, preferably C 2 to C 40 alpha-olefins preferably C 2 to C 20 alpha-olefins, preferably C 2 to C 12 alpha-olefins.
  • Preferred olefin monomers may be one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-l, 3-methylpentene-l, 3,5,5-trimethylhexene-l, and 5-ethylnonene-l.
  • the polymer produced herein is a copolymer of one or more linear or branched C 3 to C 3 o prochiral alpha-olefins or C 5 to C 3 o ring containing olefins or combinations thereof capable of being polymerized by either stereospecific and non-stereospecific catalysts.
  • Prochiral refers to monomers that favor the formation of isotactic or syndiotactic polymer when polymerized using stereospecific catalyst(s).
  • Polymers produced according to this invention are olefin polymers or "polyolefins".
  • olefin polymers is meant that at least 75 mole % of the polymer is made of hydrocarbon monomers, preferably at least 80 mole %, preferably at least 85 mole %, preferably at least 90 mole %, preferably at least 95 mole %, preferably at least 99 mole %.
  • the polymers are 100 mole % hydrocarbon monomer.
  • Hydrocarbon monomers are monomers made up of only carbon and hydrogen.
  • heteroatom containing monomers are hydrocarbon monomers where one or more hydrogen atoms have been replaced by a heteroatom.
  • the heteroatom is selected from the group consisting of chlorine, bromine, oxygen, nitrogen, silicon and sulfur, preferably the heteroatom is selected from the group consisting of oxygen, nitrogen, silicon and sulfur, preferably the heteroatom is selected from the group consisting of oxygen and nitrogen, preferably oxygen.
  • the heteroatom is not fluorine.
  • the monomers to be polymerized are not fluormonomers.
  • Fluoromonomers are defined to be hydrocarbon monomers where at least one hydrogen atom has been replaced by a fluorine atom.
  • the monomers to be polymerized are not halomonomers. (By halomonomer is meant a hydrocarbon monomer where at least one hydrogen atom is replaced by a halogen.)
  • the monomers to be polymerized are not vinyl aromatic hydrocarbons.
  • the monomers to be polymerized are preferably aliphatic or alicyclic hydrocarbons, (as defined under "Hydrocarbon” in Hawley's Condensed Chemical Dictionary, 13th edition, RJ.
  • the monomers to be polymerized are preferably linear or branched alpha-olef ⁇ ns, preferably C2 to C40 linear or branched alpha-olefins, preferably C2 to C20 linear or branched alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof, more preferably ethylene, propylene, butene hexene and octene.
  • Preferred monomers may also include aromatic-group-containing monomers containing up to 30 carbon atoms.
  • Suitable aromatic-group-containing monomers comprise at least one aromatic structure, preferably from one to three, more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety.
  • the aromatic- group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone.
  • the aromatic-group containing monomer may further be substituted with one or more hydrocarbyl groups including but not limited to C 1 to C 10 alkyl groups. Additionally two adjacent substitutions may be joined to form a ring structure.
  • Preferred aromatic-group-containing monomers contain at least one aromatic structure appended to a polymerizable olefinic moiety.
  • Particularly preferred aromatic monomers include vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially 4-phenyl-l-butene and allyl benzene.
  • Non aromatic cyclic group containing monomers are also preferred. These monomers can contain up to 30 carbon atoms.
  • Suitable non-aromatic cyclic group containing monomers preferably have at least one polymerizable olefinic group that is either pendant on the cyclic structure or is part of the cyclic structure.
  • the cyclic structure may also be further substituted by one or more hydrocarbyl groups such as, but not limited to, C 1 to C 10 alkyl groups.
  • Preferred non-aromatic cyclic group containing monomers include vinylcyclohexane, vinylcyclohexene, cyclopentadiene, cyclopentene, 4-methylcyclopentene, cyclohexene, 4- methylcyclohexene, cyclobutene, vinyladamantane, norbornene, 5- methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-butylylnorbornene, 5-pentymorbornene, 5-hexylnorbornene, 5-heptylnorbornene, 5-octyhiorbornene, 5-nonyhiorboraene, 5-decylnorbornene, 5-phenylnorbornene, vinylnorbornene,
  • Preferred diolefm monomers useful in this invention include any hydrocarbon structure, preferably C 4 to C 30 , having at least two unsaturated bonds, wherein at least one, typically two, of the unsaturated bonds are readily incorporated into a polymer by either a stereospeciflc or a non-stereospecific catalyst(s). It is further preferred that the diolefm monomers be selected from alpha-omega-diene monomers (i.e. di-vinyl monomers). More preferably, the diolefm monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms.
  • Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9- decadiene
  • Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • Preferred dienes include both cis and trans 1,4-hexadiene.
  • Non-limiting examples of preferred polar unsaturated monomers useful in this invention include nitro substituted monomers including 6-nitro-l-hexene; amine substituted monomers including N-methylallylamine, N- allylcyclopentylamine, and N-allyl-hexylamine; ketone substituted monomers including methyl vinyl ketone, ethyl vinyl ketone, and 5-hexen-2-one; aldehyde substituted monomers including acrolein, 2,2-dimethyl-4-pentenal, undecylenic aldehyde, and 2,4-dirnethyl-2,6-heptadienal; alcohol substituted monomers including allyl alcohol, 7-octen-l-ol, 7-octene-l,2-diol, 10-undecen-l-ol, 10- undecene-l,2-diol, 2-methyl-3-buten-l-ol; acetal, epoxide and or ether substituted
  • oligomers include oligomers of any C 2 to C 20 olefins, preferably C 2 to C 12 alpha-olefms, most preferably oligomers comprising ethylene, propylene and or butene are prepared.
  • a preferred feedstock for the oligomerization process is the alpha-olefin, ethylene. But other alpha-olefins, including but not limited to propylene and 1 -butene, may also be used alone or combined with ethylene.
  • Preferred alpha-olefins include any C 2 to C 40 alpha-olefin, preferably and C 2 to C 20 alpha-olefin, preferably any C 2 to C 12 alpha-olefin, preferably ethylene, propylene, and butene, most preferably ethylene.
  • Dienes may be used in the processes described herein, preferably alpha- omega-dienes are used alone or in combination with mono-alpha olefins. In a preferred embodiment the process described herein may be used to produce liomopolymers or copolymers.
  • a copolymer may comprise two, three, four or more different monomer units.
  • Preferred polymers produced herein include homopolymers or copolymers of any of the above monomers.
  • the polymer is a homopolymer of any C 2 to C 12 alpha-olefin.
  • the polymer is a homopolymer of ethylene or a homopolymer of propylene.
  • the polymer is a copolymer comprising ethylene and one or more of any of the monomers listed above.
  • the polymer is a copolymer comprising propylene and one or more of any of the monomers listed above, hi another preferred embodiment the homopolymers or copolymers described, additionally comprise one or more diolefin comonomers, preferably one or more C 4 to C 4 o diolefins.
  • the polymer produced herein is a copolymer of ethylene and one or more C 3 to C 20 linear, branched or cyclic monomers, preferably one or more C 3 to C 12 linear, branched or cyclic alpha- olefms.
  • the polymer produced herein is a copolymer of ethylene and one or more of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-l, 3-methylpentene-l, 3,5,5-trimethylhexene- 1, cyclopentene, 4-methylcyclopentene, cyclohexene, and 4-methylcyclohexene.
  • the polymer produced herein is a copolymer of propylene and one or more C 2 or C 4 to C 20 linear, branched or cyclic monomers, preferably one or more C 2 or C 4 to C 12 linear, branched or cyclic alpha-olefms.
  • the polymer produced herein is a copolymer of propylene and one or more of ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-l, 3-methylpentene-l, and 3,5,5- trimethylhexene- 1.
  • the polymer produced herein is a homopolymer of norbornene or a copolymer of norbornene and a substituted norbornene, including polar functionalized norbornenes.
  • the polymers described above further comprise one or more dienes at up to 10 weight%, preferably at 0.00001 to 1.0 weight%, preferably 0.002 to 0.5 weight%, even more preferably 0.003 to 0.2 weight%, based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 300 ppm or less.
  • the copolymers described herein comprise at least 50 mole% of a first monomer and up to 50 mole% of other monomers.
  • the polymer comprises: a first monomer present at from 40 to 95 mole%, preferably 50 to 90 mole%, preferably 60 to 80 mole %, and a comonomer present at from 5 to 60 mole%, preferably 10 to 40 mole%, more preferably 20 to 40 mole%, and a termonomer present at from 0 to 10 mole%, more preferably from 0.5 to 5 mole%, more preferably 1 to 3 mole%.
  • the first monomer comprises one or more of any C 3 to C 8 linear branched or cyclic alpha-olefins, including propylene, butene, (and all isomers thereof), pentene (and all isomers thereof), hexene (and all isomers thereof), heptene (and all isomers thereof), and octene (and all isomers thereof).
  • Preferred monomers include propylene, 1 -butene, 1 -hexene, 1 -octene, cyclopentene, cyclohexene, cyclooctene, hexadiene, cyclohexadiene and the like.
  • the comonomer comprises one or more of any C 2 to C 40 linear, branched or cyclic alpha-olefins (provided ethylene, if present, is present at 5 mole% or less), including ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, undecene, dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, 3,5,5-trimethylhexene-l, 3-methylpentene-l, 4-methylpentene-l, cyclopentadiene, and cyclohexene.
  • C 2 to C 40 linear, branched or cyclic alpha-olefins provided ethylene, if present, is present at 5 mole% or less
  • the termonomer comprises one or more of any C 2 to C 40 linear, branched or cyclic alpha-olefins, (provided ethylene, if present, is present at 5 mole% or less), including ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, undecene, dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, 3,5,5-trimethylhexene-l, 3-methylpentene-l, 4-methylpentene-l, cyclopentadiene, and cyclohexene.
  • the polymers produced by the process of the invention can be used in a wide variety of products and end-use applications.
  • Preferred polymers produced herein may have an M n (number-average molecular weight) value from 300 to 1,000,000, or between from 700 to 300,000.
  • M n number-average molecular weight
  • the polymers produced herein preferably have Mw's of 50,000 to 1 ,000,000, preferably 70,000 to 500,000.
  • preferred polymers produced herein may have a molecular weight distribution (MWD) in the range of > 1, or > 1.5 or ⁇ 8 or ⁇ 6, or ⁇ 4.
  • the polymers produced are preferably homo- and co-polymers of ethylene and or propylene and include linear low density polyethylene, elastomers, plastomers, high-density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers.
  • Polymers, typically ethylene based copolymers have a density of from 0.80g/cc to 0.97 g/cc, preferably from 0.86g/cc to 0.97g/cc; density being measured in accordance with ASTM-D-1238.
  • the polymers of this invention may be blended and/or coextruded with any other polymer.
  • Non-limiting examples of other polymers include linear low density polyethylenes, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, isotactic polypropylene, ethylene propylene copolymers and the like.
  • Polymers produced by the process of the invention and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co- extrusion as well as blow molding, injection molding, roto-molding.
  • Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing film, oriented films, and the like. Examples
  • the polymerizations for examples Sl to S7 were performed in a 0.5-liter autoclave reactor equipped with a stirrer, an external water/steam jacket for temperature control, a regulated supply of dry nitrogen, ethylene, propylene, and a septum inlet for introduction of other solvents, catalysts and scavenger solutions.
  • the polymerizations were conducted in a semi-batch mode with continuous ethylene feed.
  • the reactor was dried and degassed thoroughly prior to use. All the solvent and monomers were purified by passing through a 1 -liter basic alumina column activated at 600°C, followed by a column of molecular sieves activated at 600 0 C or Selexsorb CD column prior to transferring into the reactor.
  • the polymerization was terminated based on the total ethylene consumption. Thereafter, the reactor was cooled down and unreacted propylene and solvent were vented to the atmosphere. The resulting mixture, containing mostly solvent, polymer and unreacted monomers, was collected in a collection box and first air- dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90 0 C for about 12 hours. Stock solutions of catalyst and activator were first prepared. Then all the appropriate components were transferred into a catalyst charge tube using syringes. All of these were carried out in a drybox. The activated catalyst solution in the charge tube was flushed into the reactor using about 5 ml of toluene.
  • Examples Sl to S7 were produced using rac-dimethylsilybisindenyl hafnium dimethyl (Catalyst A) and rac-dimethylsilylbis(2-methyl-4- phenylindenyl)zirconium dimethyl (Catalyst B), following the general procedure described above.
  • the catalysts were preactivated with N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate (all the catalyst and activator were obtained from Albemarle) at a molar ratio of 1:1 to 1:1.1.
  • HFC-245fa is 1,1,1,3,3- Pentafluoropropane obtained from Honeywell under the trade name Enovate 3000.
  • the detailed conditions are listed in Table El .
  • Examples S 6 and S 7 were comparative examples produced using hexane as solvent.
  • the polymerizations for Examples S8 and S9 were carried in a liquid filled, single-stage continuous reactor.
  • the reactor was a 0.5-liter stainless steel autoclave reactor and was equipped with a stirrer, a water-cooling/steam-heating element with a temperature controller, and a pressure controller.
  • Solvents, monomers such as ethylene and propylene, and comonomers (such as butene and hexene), if present, were first purified by passing through a three-column purification system.
  • the purification system consists of an Oxiclear column (Model # RGP-Rl -500 from Labclear) followed by a 5 A and a 3 A molecular sieve columns.
  • the catalyst systems were diluted to a concentration of catalyst ranging from 0.2 to 1.4 mg/ml in toluene. All catalyst solutions were kept in an inert atmosphere with ⁇ 1.5 ppm water content and fed into reactor by metering pumps. The catalyst solution was used for all polymerization runs carried out in the same day. A new batch of catalyst solution was prepared in case that more than 700 ml of catalyst solution was consumed in one day.
  • As an impurity scavenger 250 ml of tri-n-octylaluminum (TNOA) (25 wt.% in toluene, Akzo Noble) was diluted in 22.83 kilogram of hexane.
  • TNOA tri-n-octylaluminum
  • TNOA tri-n- octylaluminum
  • the reactor was heated/cooled to the desired temperature using water/steam mixture flowing through the reactor jacket and controlled at a set pressure with controlled solvent flow. Monomers and catalyst solutions were then fed into the reactor.
  • An automatic temperature control system was used to control and maintain the reactor at a set temperature. Onset of polymerization activity was determined by observations of a viscous product and lower temperature of water-steam mixture. Once the activity was established and system reached steady state, the reactor was lined out by continuing operating the system under the established condition for a time period of at least five times of mean residence time prior to sample collection. The resulting mixture, containing mostly solvent, polymer and unreacted monomers, was collected in a collection box.
  • the collected samples were first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90 °C for about 12 hours.
  • the vacuum oven dried samples were weighed to obtain yields. AU the reactions were carried out at a pressure of 2.41 MPa-g.
  • Molecular weight (Mw, Mn, and Mz) and molecular weight distribution (Mw/Mn) of the polymers was determined using gel permeation chromatography (GPC) on a Water 150C high temperature chromatographic unit equipped with a DRI detector and four linear mixed bed columns (Polymer Laboratories PLgel Mixed-B LS, 20-micron particle size).
  • the oven temperature was at 160 0 C with the autosampler hot zone at 16O 0 C and the warm zone at 145 0 C.
  • About 0.2 wt.% of polymer sample was dissolved in 1,2,4-trichlorobenzene containing 200 ppm 2,6-di-t-butyl-4-methylphenol.
  • the flow rate was 1.0 milliliter/minute and the injection size is 100 microliters.
  • Peak melting point (Tm) and peak crystallization temperature (Tc) were determined using the following procedure according to ASTM E 794-85.
  • Differential scanning calorimetric (DSC) data was obtained using a TA Instruments model 2910 machine. Samples weighing approximately 7-10 mg were sealed in aluminum sample pans. The DSC data was recorded by first cooling the sample to -100 0 C and then gradually heating it to 200 °C at a rate of 10 °C/minute. The sample was kept at 200 0 C for 5 minutes before a second cooling-heating cycle was applied. Both the first and second cycle thermal events were recorded.
  • Ethylene content for samples produced using fluorocarbon was determined using 13 C nuclear magnetic resonance (NMR). All the peaks in the NMR spectra are referenced by setting the mmmm methyl peak to 21.8 ppm. All secondary carbons are defined by the peak regions in Table A. Naming of the peaks was made in accordance with a method by Carman, et al. in Rubber Chemistry and Technology, 44 (1971), page 781, where e.g., S ⁇ denotes a peak area of the ⁇ + secondary carbon peak.
  • tertiary carbons are defined by the peak regions in Table B (Note that the peak region of 30.7 - 31 ppm has overlapping peaks of secondary and tertiary carbons):
  • the T ⁇ and S ⁇ peaks are overlapping.
  • the area of S y7 peak can be calculated as:
  • Total area of primary carbons (P) is the total area between 19 and 23 ppm.
  • E wt% (S-T/2-P/2) / (S+T+P) (B)
  • the area under propylene band at ⁇ 1165 cm '1 and the area of ethylene band at -732 cm '1 in the spectrum were calculated.
  • the baseline integration range for the methylene rocking band is nominally from 695 cm “1 to the minimum between 745 and 775 cm “1 .
  • the baseline and integration range is nominally from 1195 to 1126 cm “1 .
  • AR is the ratio of the area for the peak at ⁇ 1165 cm “1 to the area of the peak at ⁇ 732 cm “1 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de polymérisation multiphase pour la production d'oléfines, procédé consistant à mettre en contact des oléfines avec un catalyseur homogène, ou un système de catalyseur homogène, à une température comprise entre le point de fusion du polymère anhydre, et 80 °C en dessous du point de fusion du polymère anhydre en présence d'un hydrocarbure fluoré. L'invention concerne également un procédé de production de polyéthylène consistant à mettre en contact un catalyseur homogène ou un système de catalyseur homogène avec de l'éthylène et 0 à 40 % en poids d'un ou plusieurs comonomères oléfiniques en C3 à C40, en présence d'un hydrocarbure fluoré et, éventuellement, d'un solvant hydrocarburé, à une température inférieure au point de fusion du milieu réactionnel. L'invention concerne en outre un procédé de production de polypropylène consistant à mettre en contact un catalyseur homogène ou un système de catalyseur homogène avec du propylène et 0 à 50 % en poids d'un ou plusieurs comonomères d'éthylène et d'oléfines en C4 à C40, en présence d'un hydrocarbure fluoré et, éventuellement, d'un solvant hydrocarburé, à une température inférieure au point de fusion du milieu réactionnel.
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US7342079B2 (en) 2004-06-21 2008-03-11 Exxonmobil Chemical Patents Inc. Polymerization process and reactor system
US7351779B2 (en) 2005-11-22 2008-04-01 Exxonmobil Chemical Patents Inc. Polymerization process and reactor system
US7419958B2 (en) 2001-03-26 2008-09-02 Dana-Farber Cancer Institute, Inc. Method of attenuating reactions to skin irritants
US7423103B2 (en) 2004-06-21 2008-09-09 Exxonmobil Chemical Patents Inc. Low fouling and high activity polymerization process
US7449530B2 (en) 2004-06-21 2008-11-11 Exxonmobil Chemical Patents Inc. Polymerization process
US7459510B2 (en) 2004-06-21 2008-12-02 Exxonmobil Chemical Patents Inc. Polymerization process
US7491776B2 (en) 2004-06-21 2009-02-17 Exxonmobil Chemical Patents Inc. Polymerization process
US7691956B2 (en) 2004-06-21 2010-04-06 Exxonmobil Chemical Patents Inc. Polymerization process
US7700699B2 (en) 2004-06-21 2010-04-20 Exxonmobil Chemical Patents Inc. Polymerization process
US7728084B2 (en) 2004-06-21 2010-06-01 Exxonmobil Chemical Patents Inc. Polymerization process
US7741420B2 (en) 2004-07-14 2010-06-22 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7858714B2 (en) 2004-06-21 2010-12-28 Exxonmobil Chemical Patents Inc. Polymerization process
US7858719B2 (en) 2004-05-20 2010-12-28 Exxonmobil Chemical Patents Inc. Polymerization process
WO2020123971A1 (fr) * 2018-12-14 2020-06-18 Dow Global Technologies Llc Processus de polymérisation en solution
WO2020123973A1 (fr) * 2018-12-14 2020-06-18 Dow Global Technologies Llc Processus de polymérisation en solution
CN114989340A (zh) * 2022-06-28 2022-09-02 杭州双安科技有限公司 一种烯烃聚合方法
CN115612010A (zh) * 2021-07-13 2023-01-17 中化学科学技术研究有限公司 一种制备聚烯烃的方法和装置

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EP0369727A1 (fr) * 1988-11-17 1990-05-23 AUSIMONT S.p.A. Procédé de préparation de copolymères de tetrafluoroéthylène-éthylène

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US3470143A (en) * 1964-03-26 1969-09-30 Dart Ind Inc Highly fluorinated hydrocarbons used as diluents in the polymerization of ethylenically unsaturated monomers
EP0369727A1 (fr) * 1988-11-17 1990-05-23 AUSIMONT S.p.A. Procédé de préparation de copolymères de tetrafluoroéthylène-éthylène

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7419958B2 (en) 2001-03-26 2008-09-02 Dana-Farber Cancer Institute, Inc. Method of attenuating reactions to skin irritants
US7858719B2 (en) 2004-05-20 2010-12-28 Exxonmobil Chemical Patents Inc. Polymerization process
US7449530B2 (en) 2004-06-21 2008-11-11 Exxonmobil Chemical Patents Inc. Polymerization process
US7728084B2 (en) 2004-06-21 2010-06-01 Exxonmobil Chemical Patents Inc. Polymerization process
US7342079B2 (en) 2004-06-21 2008-03-11 Exxonmobil Chemical Patents Inc. Polymerization process and reactor system
US7459510B2 (en) 2004-06-21 2008-12-02 Exxonmobil Chemical Patents Inc. Polymerization process
US7491776B2 (en) 2004-06-21 2009-02-17 Exxonmobil Chemical Patents Inc. Polymerization process
US7691956B2 (en) 2004-06-21 2010-04-06 Exxonmobil Chemical Patents Inc. Polymerization process
US7700699B2 (en) 2004-06-21 2010-04-20 Exxonmobil Chemical Patents Inc. Polymerization process
US7423103B2 (en) 2004-06-21 2008-09-09 Exxonmobil Chemical Patents Inc. Low fouling and high activity polymerization process
US7858714B2 (en) 2004-06-21 2010-12-28 Exxonmobil Chemical Patents Inc. Polymerization process
US7741420B2 (en) 2004-07-14 2010-06-22 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7351779B2 (en) 2005-11-22 2008-04-01 Exxonmobil Chemical Patents Inc. Polymerization process and reactor system
WO2020123971A1 (fr) * 2018-12-14 2020-06-18 Dow Global Technologies Llc Processus de polymérisation en solution
WO2020123973A1 (fr) * 2018-12-14 2020-06-18 Dow Global Technologies Llc Processus de polymérisation en solution
CN115612010A (zh) * 2021-07-13 2023-01-17 中化学科学技术研究有限公司 一种制备聚烯烃的方法和装置
CN115612010B (zh) * 2021-07-13 2024-03-26 中化学科学技术研究有限公司 一种制备聚烯烃的方法和装置
CN114989340A (zh) * 2022-06-28 2022-09-02 杭州双安科技有限公司 一种烯烃聚合方法

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