Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/022—Boron compounds without C-boron linkages
• • 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
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

• TECHNICAL FIELD This invention relates to the preparation of olefin polymers using catalyst systems based on ionic cocatalysts for organometallic or organometalloid catalyst complexes where the cocatalysts comprise carbenium-based cations and noncoordinating or weakly coordinating anions BACKGROUND ART
• noncoordinating anion is now accepted terminology in the field of olefin and vinyl monomer polymerization, both by coordination or insertion polymerization and carbocationic polymerization See, for example, EP 0 277 003, EP 0 277 004, U S Patent 5,198,401, U S Patent 5,278,1 19, Baird, Michael C , et al, J Am Chem Soc.
• noncoordinating anions are described to function as electronic stabilizing cocatalysts, or counterions, for essentially cationic metallocene complexes which are active for polymerization
• the term noncoordinating anion as used here applies both to truly noncoordinating anions and coordinating anions that are at most weakly coordinated to the cationic complex so as to be labile to replacement by olefinically or acetylenically unsaturated monomers at the insertion site
• These noncoordinating anions can be effectively introduced into a polymerization medium, or premixed with an organometallic catalyst compound prior to introduction into the polymerization medium, as Bronsted acid salts containing charge-balancing count ercations, ionic cocatalyst compounds See also, the review articles by S H Strauss, "The Search for Larger and More Weakly Coordinating An
• Patent 5,198,401 describes catalyst activator compounds represented by the formula [(L'-H) + ]d[(M') m+ Q 1 Q 2 . . .Q impart] d ⁇ where L' is a neutral base, H is a hydrogen atom and [(M')'" + Q ⁇ Q 2 . . .Q occasion] is a metal or metalloid atom subtended by a variety of ligands, preferably where M is boron and two or more of Qtile are aromatic radicals, such as phenyl, napthyl and anthracenyl, each preferably fluorinated. L' is illustrated with various trialkyl- substituted ammonium complexes and N,N-dialkylanilinium complexes.
• WO 97/35893 describes cocatalyst activator compounds represented by the formula
• L* includes nitrogen containing neutral Lewis bases
• B is boron in an oxidation state of 3
• Q' is a fluorinated Cj. 2 o hydrocarbyl group, preferably a fluorinated aryl group.
• the cocatalyst compounds are said to be rendered soluble in aliphatic solvents by incorporation of olephilic groups, such as long chain alkyl or substituted-alkyl groups, into the Bronsted acid L*.
• EP 0 426 637 describes the use of the cocatalyst compound non- substituted triphenylcarbenium tetrakis(pentafluorophenyl)boronate as a proton- free ionizing agent that abstracts a metal ligand to form a catalytically active metallocene cation and a loosely coordinated anion.
• Patent 5,502,017 addresses ionic metallocene catalysts for olefin polymerization comprising, as a cocatalyst component, a weakly coordinating anion comprising boron substituted with halogenated aryl substituents preferably containing silylalkyl substitution, such as para-silyl-t-butyldimethyl. This substitution is said to increase the solubility and thermal stability of the resulting metallocene salts.
• Examples 3-5 describe the synthesis and polymerization use of the cocatalyst compound triphenylcarbenium tetrakis (4-dimethyl-t-butylsilyl-2, 3, 5, 6- tetrafluorophenyl)borate.
• Olefin solution polymerization processes are generally conducted in aliphatic solvents that serve both to maintain reaction medium temperature profiles and solvate the polymer products prepared.
• aryl-group contaimng activators such as those having phenyl derivatives and other fused or pendant aryl-group substituents, are at best sparingly soluble in such solvents and typically are introduced in aryl solvents such as toluene Solution polymerization processes in aliphatic solvents thus can be contaminated with toluene that must be removed to maintain process efficiencies and to accommodate health-related concerns for both industrial manufacturing processes and polymer products from them
• relatively insoluble catalyst components can be introduced via slurry methods, but such methods required specialized handling and pumping procedures that complicate and add significant costs to industrial scale plant design and operation Low solubility can also become disadvantageous should the process involve low temperature operation at some stage such as in typical adiabatic processes run in areas subject to low ambient temperatures Additionally, separating or counteracting the build up in the recycle system of aromatic catalyst solvents may
• This invention addresses a process for the preparation of polyolefins from one or more olefinic monomers comprising combining under polymerization conditions said olefins with the reaction product of l) a transition metal organometallic catalyst compound and n) a cocatalyst complex comprising a t ⁇ alkylsilyl-substituted carbenium cation and a noncoordinating or weakly coordinating anion
• the cocatalysts of the invention provide carbon compound by-products and weakly coordinating, stabilizing anions for essentially cationic transition metal organometallic catalyst complexes that exhibit high polymerization activities DETAILED DESCRIPTION OF THE INVENTION
• the invention provides a process for olefin polymerization in which anion- containing cocatalyst complexes and organometallic catalyst precursor compounds can be combined to form active catalysts for olefin polyme ⁇ zation Subsequent contacting, or in situ catalyst formation essentially concurrent with said contacting, with insertion polymerizable monomers, those having accessible olefimc, acetylenic unsaturation, or with monomers having olefinic unsaturation capable of cationic polyme ⁇ zation
• the catalyst according to the invention is suitable for preparing polymers and copolymers from olefinically and acetylemcally unsaturated monomers
• the invention cocatalyst complexes can be represented by the following formula
• [A] is a halogenated, tetraryl-substituted Group 10-15 non-carbon, element-based anion, especially those that are have fluorine groups substituted for hydrogen atoms on the aryl groups , or on alkyl substituents on those aryl groups
• t ⁇ alkylsilyl group-substituted phenyl groups may be independently selected from the groups depicted below
• the effective Group 8-15 element cocatalyst complexes of the invention are, in a preferable embodiment, derived from an ionic salt, comprising a 4- coordinate Group 10-14 element anionic complex, where A ⁇ can be represented as: where M is one or more Group 10-15 metalloid or metal, preferably boron or aluminum, and either each Q is ligand effective for providing electronic or steric effects rendering [(M')Q ⁇ Q2 • Q suitcase] " suitable as a noncoordinating anion as that is understood in the art, or a sufficient number of Q are such that [(M')Q ! Q 2 . . .Q adjunct] " as a whole is an effective noncoordinating or weakly anion.
• Exemplary Q substituents specifically include fluorinated aryl groups, preferably perfluorinated aryl groups, and include substituted Q groups having substituents additional to the fluorine substitution, such as fluorinated hydrocarbyl groups.
• Preferred fluorinated aryl groups include phenyl, biphenyl, napthyl and derivatives thereof.
• one Q group, or ligand, of the anionic complex may also be bonded to a metal/metalloid oxide support or polymeric support.
• Metal or metalloid oxide supports of the described bonding method for the invention include any metal/metalloid oxides, preferably those having surface hydroxyl groups exhibiting a pKa equal to or less than that observed for amorphous silica, i.e., pKa less than or equal to about 1 1. Accordingly any of the conventionally known silica support materials that retain hydroxyl groups after dehydration treatment methods will be suitable in accordance with the invention.
• silica and silica containing metal oxide based supports are preferred.
• Silica particles, gels and glass beads are most typical.
• Polyme ⁇ c supports are preferably hydroxyl-functional -group-containing polymeric substrates, but functional groups may be any of the primary alkyl amines, secondary alkyl amines, and others, where the groups are structurally incorporated in a polyme ⁇ c chain and capable of a acid-base reaction with the Lewis acid such that a ligand filling one coordination site of the Group 13 element is protonated and replaced by the polymer incorporated functionality See, for example, the functional group containing polymers of U S Patent 5,288,677, the functionahzed polymers of U S Patents 5,427,991 and the descriptions in copending applications U S Serial No 09/277,339, filed 26 March 1999, and its equivalent PCT/99US/06135, and U S Serial No 09/092,752, filed 5 June 1998, and its equivalent WO 98
• catalyst complexes of the invention may also physically deposited on or affixed to a suitable support material See, for example, the teachings of WO 91/09882, WO 93/11172, WO 96/35726 and U S Patents 4,463,135, and 5,610,115
• Transition metal compounds suitable as olefin polymerization catalysts by coordination or insertion polymerization in accordance with the invention will include the known organometallic transition metal compounds useful in traditional Ziegler-Natta coordination polymerization, particularly the metallocene compounds known to be useful in coordination polymerization, when such compounds are capable of catalytic activation by the cocatalyst activators described for the invention These will typically include Group 3-10 transition metal compounds wherein at least one metal ligand can be abstracted by the cocatalyst activators, particularly those hgands including hydride, hydrocarbyl, and hydrocarbylsilyl, and lower alkyl-substituted (Ci-Cio) derivatives of those Ligands capable of abstraction and transition metal compounds comprising them include those metallocenes described in the background art, see for example US
• Patents 5,198,401 and WO 92/00333 Syntheses of these compounds are well known from the published literature Additionally, where the metal ligands include halogen, amido or alkoxy moieties (for example, biscyclopentadienyl zirconium dichloride) which are not capable of abstraction with the activating cocatalysts of the invention, they can be converted into suitable ligands via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See also EP-A1-0
• metallocene compounds which comprise, or can be alkylated to comprise, at least one ligand capable of abstraction to form a catalytically active transition metal cation appear in the patent literature, e.g., EP- A-0 129 368, U. S. Patents 4,871,705, 4,937,299, 5,324,800 EP-A-0 418 044, EP- A-0 591 756, WO-A-92/00333, WO-A-94/01471 and WO 97/22635.
• Such metallocene compounds can be described for this invention as mono- or biscyclopentadienyl substituted Group 3, 4, 5, or 6 transition metal compounds wherein the ancillary ligands may be themselves substituted with one or more groups and may be bridged to each other, or may be bridged through a heteroatom to the transition metal.
• the size and constituency of the ancillary ligands and bridging elements are not critical to the preparation of the ionic catalyst systems of the invention but should be selected in the literature described manner to enhance the polymerization activity and polymer characteristics being sought.
• the cyclopentadienyl rings when bridged to each other, will be lower alkyl-substituted (Ci- C ⁇ ) in the 2 position (without or without a similar 4-position substituent in the fused ring systems) and may additionally comprise alkyl, cycloalkyl, aryl, alkylaryl and or arylalkyl substituents, the latter as linear, branched or cyclic structures including multi-ring structures, for example, those of U.S. Patents 5,278,264 and 5,304,614.
• substituents should each have essentially hydrocarbyl characteristics and will typically contain up to 30 carbon atoms but may be heteroatom containing with 1-5 non-hydrogen/carbon atoms, e.g., N, S, O, P, Ge, B and Si. All documents are incorporated by reference for purposes of U.S. patent practice.
• Metallocene compounds suitable for the preparation of linear polyethylene or ethylene-containing copolymers are essentially any of those known in the art, see again
• Representative metallocene compounds can have the formula:
• L is a substituted cyclopentadienyl or heterocyclopentadienyl ancillary ligand ⁇ -bonded to M;
• L B is a member of the class of ancillary ligands defined for L A , or is J, a heteroatom ancillary ligand ⁇ -bonded to M; the L A and L B ligands may be covalently bridged together through one or more Group 13-16 element- containing linking groups;
• L c is an optional neutral, non-oxidizing ligand having a dative bond to M (i equals 0 to 3), M is a Group 4 or 5 transition metal, and, D and E are independently monoanionic labile ligands, each having a ⁇ -bond to M, optionally bridged to each other or L ⁇ or L B , which can be broken for abstraction purposes by a suitable activator and into which a polymerizable monomer or macromonomer can insert for coordination poly
• Representative traditional Ziegler-Natta transition metal compounds include tetrabenzyl zirconium, tetra b ⁇ s(t ⁇ methyls ⁇ lylmethyl) zirconium, oxot ⁇ s(t ⁇ methls ⁇ lylmethyl) vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, b ⁇ s(hexamethyl d ⁇ s ⁇ laz ⁇ do)d ⁇ methyl titanium, t ⁇ s(t ⁇ methyl silyl methyl) niobium dichlo ⁇ de, tr ⁇ s(tr ⁇ methyls ⁇ lylmethyl) tantalum dichlo ⁇ de
• the important features of such compositions for coordination polymerization are the ligand capable of abstraction and that ligand into which the ethylene (olefinic) group can be inserted These features enable the ligand abstraction from the transition metal compound and the concomitant formation of the ionic catalyst composition of the invention
• Additional organometallic transition metal compounds suitable as olefin polymerization catalysts in accordance with the invention will be any of those Group 3-11 that can be converted by ligand abstraction into a catalytically active cation and stabilized in that active electronic state by a noncoordinating or weakly coordinating anion sufficiently labile to be displaced by an olefinically unsaturated monomer such as ethylene
• Exemplary compounds include those described in the patent literature International Patent Publications WO 96/23010, WO 97/48735 and
• Bridged bis(arylamido) Group 4 compounds for olefin polymerization are described by D. H. McConville, et al, in Organometallics 1995, 14, 5478- 5480. Synthesis methods and compound characterization are presented. Further work appearing in D. H. McConville, et al, Macromo/ecules 1996, 29, 5241-5243, described bridged bis(arylamido) Group 4 compounds that are active catalysts for polymerization of 1-hexene. Additional transition metal compounds suitable in accordance with the invention include those described in WO 96/40805. Cationic Group 3 or Lanthanide metal complexes for coordination polymerization of olefins is disclosed in copending U.S. application Serial number 09/408050, filed
• the precursor metal compounds are stabilized by a monoanionic bidentate ancillary ligand and two monoanionic ligands and are capable of activation with the ionic cocatalysts of the invention.
• organometallic or organometalloid catalyst precursor compounds may be found in the literature, any of such will be suitable where comprising, or where capable of alkylation to comprise, ligands capable of ionizing abstraction. See, for instance, N. C. Gibson, et al, "The Search for New-Generation Olefin Polymerization Catalysts: Life Beyond Metallocenes", Angew. Chem. Int. Ed, 38, 428-447 (1999).
• the total catalyst system will generally additionally comprise one or more organometallic compound.
• organometallic compound Such compounds as used in this application and its claims is meant to include those compounds effective for removing polar impurities from the reaction environment and for increasing catalyst activity.
• Impurities can be inadvertently introduced with any of the polymerization reaction components, particularly with solvent, monomer and catalyst feed, and adversely affect catalyst activity and stability. It can result in decreasing or even elimination of catalytic activity, particularly when ionizing anion pre-cursors activate the catalyst system.
• the polar impurities, or catalyst poisons include water, oxygen, metal impurities, etc.
• steps are taken before provision of such into the reaction vessel, for example by chemical treatment or careful separation techniques after or during the synthesis or preparation of the various components, but some minor amounts of organometallic compound will still normally be used in the polymerization process itself. Typically these compounds will be organometallic compounds such as the
• Exemplary compounds include triethyl aluminum, triethyl borane, triisobutyl aluminum, methylalumoxane, and isobutyl aluminumoxane.
• Those compounds having bulky or C 6 -C o linear hydrocarbyl substituents covalently bound to the metal or metalloid center being preferred to minimize adverse interaction with the active catalyst.
• Examples include triethylaluminum, but more preferably, bulky compounds such as triisobutylaluminum, triisoprenylaluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n- octylaluminum, or tri-n-dodecylaluminum.
• bulky compounds such as triisobutylaluminum, triisoprenylaluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n- octylaluminum, or tri-n-dodecylaluminum.
• Alumoxanes also may be used in scavenging amounts with other means of activation, e.g., methylalumoxane and triisobutyl-aluminoxane with boron-based activators.
• the amount of such compounds to be used with catalyst compounds of the inventions is minimized during polymerization reactions to that amount effective to enhance activity (and with that amount necessary for activation of the catalyst compounds if used in a dual role) since excess amounts may act as catalyst poisons.
• the catalyst complexes of the invention are useful in polymerization of unsaturated monomers conventionally known to be polymerizable under coordination polymerization using metallocenes. Such conditions are well known and include solution polymerization, slurry polymerization, gas-phase polymerization, and high-pressure polymerization.
• the catalyst of the invention may be supported (preferably as described above) and as such will be particularly useful in the known operating modes employing fixed-bed, moving-bed, fluid- bed, slurry or solution processes conducted in single, series or parallel reactors.
• Pre-polymerization of supported catalyst of the invention may also be used for further control of polymer particle morphology in typical slurry or gas phase reaction processes in accordance with conventional teachings.
• the catalyst system is employed in liquid phase (solution, slurry, suspension, bulk phase or combinations thereof), in high-pressure liquid or supercritical fluid phase, or in gas phase.
• 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 invention copolymers.
• Hydrocarbyl solvents are suitable, both aliphatic and aromatic, hexane is preferred.
• Bulk and slurry processes are typically done by contacting the catalysts with a slurry of liquid monomer, the catalyst system being supported.
• Gas phase processes typically use a supported catalyst and are conducted in any manner known to be suitable for ethylene homopolymers or copolymers prepared by coordination polymerization.
• Illustrative examples may be found in U.S. Patents 4,543,399, 4,588,790, 5,028,670, 5,382,638, 5352,749, 5,408,017, 5,436,304, 5,453,471, and 5,463,999, 5,767,208 and WO 95/07942.
• Each is incorporated by reference for purposes of U.S. patent practice.
• the polymerization reaction temperature can vary from about 40°C to about 250°C.
• the polymerization reaction temperature will be from 60°C to 220°.
• the pressure can vary from about 1 mm Hg to 2500 bar, preferably from 0.1 bar to 1600 bar, most preferably from 1.0 to 500 bar.
• the invention is hence especially suitable for use with solution polymerization using bridged fluorenyl systems and/or naphthyl containing non- coordinating anions optimized for higher temperature and/or higher molecular weight production at temperature in excess of 130 or even 170 degrees C and up to 250 degrees C.
• Linear polyethylene including high and ultra-high molecular weight polyethylenes, including both homo- and copolymers with other alpha-olefin monomers, alpha-olefinic and/or non-conjugated diolefins, for example, C 3 -C 0 olefins, diolefins or cyclic olefins, are produced by adding ethylene, and optionally one or more of the other monomers, to a reaction vessel under low pressure (typically ⁇ 50 bar), at a typical temperature of 40-250 °C with the invention catalyst that has been slurried with a solvent, such as hexane or toluene. Heat of polymerization is typically removed by cooling.
• a solvent such as hexane or toluene
• Gas phase polymerization can be conducted, for example, in a continuous fluid bed gas- phase reactor operated at 2000-3000 kPa and 60-160 °C, using hydrogen as a reaction modifier (100-200 PPM), C 4 -C 8 comonomer feedstream (0 5-1 2 mol%), and C 2 feedstream (25-35 mol%)
• hydrogen as a reaction modifier (100-200 PPM)
• C 4 -C 8 comonomer feedstream (0 5-1 2 mol%)
• C 2 feedstream 25-35 mol%)
• Ethylene- ⁇ -olefin including ethylene-cychc olefin and ethylene- ⁇ -olefin- diolef ⁇ n
• elastomers of high molecular weight and low crystallmity can be prepared utilizing the catalysts of the invention under traditional solution polymerization processes or by introducing ethylene gas into a slurry utilizing the ⁇ -olefin or cyclic olefin or mixture thereof with other monomers
• Typical ethylene pressures will be between 10 and 1000 psig (69-6895 kPa) and the polymerization diluent temperature will typically be between 40 and 160 °C
• the process can be carried out in a stirred tank reactor, or more than one operated in series or parallel See the general disclosure of U S Patent 5,001,205 for general process conditions See also, International Applications WO 96/33227 and WO 97/22639 All documents are incorporated by reference for description of polymerization processes, metallocene selection and useful scavenging compounds
• olefinically unsaturated monomers besides those specifically described above may be polymerized using the catalysts according to the invention, for example, styrene, alkyl-substituted styrenes, isobutylene and other geminally disubstituted olefins, ethyhdene norbornene, norbornadiene, dicyclopentadiene, and other olefimcally-unsaturated monomers, including other cyclic olefins, such as cyclopentene, norbornene, alkyl-substituted norbornenes, and vinyl group-containing polar monomers capable of coordination polymerization See, for example, U S Patents 5,635,573, 5,763,556, and WO 99/30822 Additionally, alpha-olefinic macromonomers of up to 1000 mer units, or more, may also be incorporated by copolyme ⁇ zation yielding branch- containing olefin polymers Additionally
• the catalyst compositions of the invention can be used as described above individually for coordination polymerization or can be mixed to prepare polymer blends with other known olefin polyme ⁇ zation catalyst compounds
• polymer blends can be prepared under polymerization conditions analogous to those using individual catalyst compositions Polymers having increased MWD for improved processing and other traditional benefits available from polymers made with mixed catalyst systems can thus be achieved
• blended polymers can be achieved ex situ through mechanical blending or in situ through the use of a mixed catalyst system It is generally believed that in situ blending provides a more homogeneous product and allows the blend to be produced in one step
• mixed catalyst systems for in situ blending involves combining more than one catalyst in the same reactor to simultaneously produce multiple distinct polymer products This method requires additional catalyst synthesis and the various catalyst components must be matched for their activities, the polymer products they generate at specific conditions, and their response to changes in polymerization conditions
• Example 2a Polymerization Reaction
• the general of la was conducted with an organometallic catalyst precursor substitution A 5 0 x 10 _ 5 M r c-Me Si(Ind) 2 HfMe solution in hexane was in used place of the Cat solution in example la
• Example 2b Polymerization Reaction
• Example 4b Polymerization Example: Act [((3, 5-(Et3Si) 2 -Ph) 3 C]+ [(pfp) + B] "
• Example 4c Comparative Example: Act [Ph 3 C] + [B(C 6 F 5 ) ] ⁇
• the procedure of example la was followed with an activator compound substitution: A mixture of tritylcarbenium tetrakis(pentafluorophenyl)borate,

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