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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F110/06—Propene
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F210/06—Propene
• • C—CHEMISTRY; METALLURGY
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/941—Synthetic resins or natural rubbers -- part of the class 520 series having the transition metal bonded directly to carbon
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• This disclosure relates to catalyst systems for olefin polymerization.
• this disclosure relates to metallocene catalyst systems and polymers produced therefrom.
• Olefin polymers and copolymers such as polyethylene, polypropylene and ethylene-propylene can be produced under various polymerization conditions and employing various polymerization catalysts.
• the resulting polymer may exhibit stereoregularity.
• a polypropylene product may be isotactic wherein each methyl group attached to the tertiary carbon atoms of the successive monomeric unit falls on the same side of a hypothetical plane through the main chain of the polymer.
• Polypropylene may also be syndiotactic wherein the methyl groups attached to the tertiary carbon atoms of the successive monomeric unit are arranged as racemic dyads.
• the methyl groups in isotactic polypropylene lie on the same side of the polymer backbone whereas in syndiotactic polypropylene the methyl groups lie on alternate sides of the polymer backbone.
• the polymer is atactic.
• the stereoregularity of the polymeric product impacts both the physical and mechanical properties of said product.
• Fluorenyl-type metallocene catalysts are effective catalysts in the polymerization of olefin polymers such as ethylene, propylene and higher olefins or other ethylenically unsaturated monomers into homopolymers or copolymers.
• Fluorenyl-type metallocenes are generally characterized by bridged cyclopentadienyl and fluorenyl groups that serve as a ligand to a metal atom. Varying the substituents or position of substituents on the fluorenyl group, cyclopentadienyl group or bridging moiety of a given fluorenyl-type metallocene catalyst may produce polymers having very different physical properties.
• an isomer of a fluorenyl-type metallocene catalyst may produce isotactic polypropylene, while another isomer of the catalyst may produce syndiotactic polypropylene.
• properties such as the molecular weight and melting points of the polypropylene composition may vary and as a result the mechanical properties and utility of the polymer may vary.
• an olefin polymerization process comprising contacting one or more olefins and a catalyst component in a reaction zone under suitable reaction conditions to form a polyolefm, wherein the catalyst component is characterized by the formula:
• B(Cp)(Fl)MQ 2 wherein M comprises a metal, Q comprises a halogen, an alkyl group or an aryl group or combinations thereof, Cp comprises a cyclopentadienyl group, Fl comprises a fluorenyl group, B is a bridging group that may be characterized by the general formula -YRH wherein Y comprises C or Si and R comprises an alkyl group, an aryl group, a poly-aryl group or combinations thereof.
• Figure 1 is a plot of catalyst activity versus ethylene concentration in feed.
• Figure 2 is a plot of percent ethylene in the feed versus melt flow temperatures for polymers produced using Catalyst A.
• Figure 3 is a plot of hydrogen concentration versus catalyst activity for
• Figure 4 is a plot of catalyst activity versus polymer molecular weight for
• Figure 5 is a plot of hydrogen concentration versus molecular weight of the polymer for Catalyst E.
• Figure 6 is a plot of the concentration of ethylene in the feed versus catalyst activity for Catalyst E.
• Figure 7 is a plot the concentration of ethylene in the feed versus the polymer molecular weight for polymers produced using Catalyst E.
• Figure 8 is a plot of concentration of ethylene in the feed versus concentration of ethylene in the copolymer composition for polymers produced using
• Figure 9 is a plot of the comparative melting temperature of isotactic polypropylene produced by several different metallocene catalysts.
• Figure 10 is a plot of the comparative molecular weight of isotactic polypropylene produced by several different metallocene catalysts.
• Figure 11 is a plot of the comparative molecular weight of a random ethylene/propylene copolymer produced by several different metallocene catalysts.
• Figure 12 is a plot of the comparative melting temperatures of a random ethylene/propylene copolymer produced by several different metallocene catalysts.
• Figure 13 is a plot of the concentration of ethylene in the feed versus catalyst activity for a random ethylene/propylene copolymer produced using Catalyst H.
• Figure 14 is a plot of the concentration of ethylene in the feed versus the polymer molecular weight for a random ethylene/propylene copolymer produced using
• Figure 15 is a plot of the concentration of ethylene in the feed versus the polymer melting temperature for a random ethylene/propylene copolymer produced using Catalyst H.
• Figure 16 is a plot of the concentration of ethylene in the feed versus the percent xylene solubles of the polymer composition for a random ethylene/propylene copolymer produced using Catalyst H.
• Figure 17 is a plot of the effect of the hydrogen concentration on the melting points of the polymers produced using Catalyst K.
• Figure 18 is a plot of the effect of the hydrogen concentration on the melt flow of the polymer produced using Catalyst K.
• Figure 19 is a plot of ethylene concentration in the feed versus the catalyst activity for an ethylene/propylene random copolymer produced using Catalyst
• Figure 20 is a plot of the ethylene concentration in the feed versus the melt flow of the polymeric composition for an ethylene/propylene random copolymer produced using Catalyst K.
• Figure 21 is a plot of the ethylene concentration in the polymeric composition versus the melting temperature of the polymer for an ethylene/propylene random copolymer produced using Catalyst K.
• Figure 22 is a plot of the ethylene concentration in the feed versus the ethylene concentration in the polymeric composition for an ethylene/propylene random copolymer produced using Catalyst K.
• substituted refers to an atom, radical or group replacing hydrogen in a chemical compound.
• homogenous polymerization refers to polymerization via contact with a catalyst that is present within the reaction system in the same phase as the reactants (e.g., a catalyst in solution within a liquid phase reaction.)
• the term "tacticity” refers to the arrangement of pendant groups in a polymer.
• a polymer is “atactic” when its pendant groups are arranged in a random fashion on both sides of the chain of the polymer.
• a polymer is
• isotacticity is measured via 13 C NMR spectroscopy using meso pentads and is expressed as percentage of meso pentads (%mmmm).
• meso pentads refers to successive methyl groups located on the same side of the polymer chain.
• molecular weight distribution is the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of a polymer and may also be referred to as the polydispersity index.
• melting temperature is measured by differential scanning calorimetry using a modified version of ASTM D 3418-99. Specifically, for a sample weighing between 5 and 1O g, the following standard test conditions involved heating the sample from 50 0 C to 210 0 C to erase the thermal history of the sample, followed by holding the sample at 210 0 C for 5 minutes. The sample is then cooled to 50 0 C to induce recrystallization and subsequently subjected to a second melt in the temperature range 50 0 C to 190 0 C. For each of these temperature changes, the temperature is ramped at a rate of 10 °C/min.
• a catalyst system herein refers to one or more chemical agents, which operate in concert to increase the rate of a reaction.
• Said catalyst system may comprise a metallocene catalyst.
• Metallocene catalysts may be characterized generally as coordination compounds incorporating one or more cyclopentadienyl (Cp) groups (which may be substituted or unsubstituted, each substitution being the same or different) coordinated with a transition metal through ⁇ bonding.
• a catalyst for use in olefin polymerization comprises at least one cyclopentadienyl ligand, at least one fluorenyl ligand, at least one bridging ligand and at least one metal. These catalysts are collectively referred to herein as fluorenyl metallocene catalysts (FMC). Each of the components of the FMCs will be described in more detail herein.
• the FMC may be used in conjunction with one or more cocatalysts to produce a catalyst system that effects the polymerization of olefins such as alpha olefins to produce homopolymers or copolymers of said olefins.
• the disclosed catalysts may be employed in the production of stereoregular polymer products such as isotactic polypropylene.
• a FMC for the polymerization of olefins may be represented by the general formula:
• B(Cp)(Fl)MQ 2 where M comprises a metal, Q may comprise a halogen, an alkyl group, an aryl group, or combinations thereof, Cp is a cyclopentadienyl group, Fl is a fluorenyl group, and B is a structural bridge between Cp and Fl imparting stereorigidity to said catalyst.
• Q may comprise a halogen, an alkyl group, an aryl group, or combinations thereof
• Cp is a cyclopentadienyl group
• Fl is a fluorenyl group
• B is a structural bridge between Cp and Fl imparting stereorigidity to said catalyst.
• B, Q, Fl or any combination thereof may be substituted.
• B, Q, Fl or any combination thereof may be unsubstituted as will be described in detail later herein.
• a FMC for the polymerization of olefins comprises a cyclopentadienyl group (Cp).
• the Cp group is unsubstituted, alternatively the Cp is substituted.
• the Cp group may have any number and/or placement of substituent groups capable of producing the desired polymer product.
• the substituents on the Cp may comprise an aliphatic group; an aromatic group; a cyclic group; any combination thereof or any substituted derivative thereof, including but not limited to, a halide, an alkoxide, or an amide-substituted derivative thereof; any one of which has from 1 to 20 carbon atoms; or hydrogen.
• aliphatic groups include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each instance having from one to 20 carbon atoms.
• aliphatic groups include, but are not limited to, hydrocarbyls such as paraffins and alkenyls.
• Cp substituent groups may be the same or different and may include hydrogen radicals, alkyls (e.g., methyl, ethyl, propyl, butyl (e.g., tert-butyl,) pentyl, hexyl, fluoromethyl, fluoroethyl, difluroethyl, iodopropyl, bromohexyl, benzyl, phenyl, methylphenyl, tert-butylphenyl, chlorobenzyl, dimethylphosphine and methylphenylphosphine), alkenyls (e.g., 3-butenyl, 2-propenyl and 5-hexenyl), alkynyls, cycloalkyls (e.g., cyclopentyl and cyclohexyl), aryls (e.g., trimethylsilyl, trimethylgermyl, methyldiethylsily
• a FMC for the polymerization of olefins comprises a fluorenyl group (Fl).
• Fluorenyl groups may be characterized by the chemical formula and numbering scheme indicated in Formula (I):
• 9 indicates the bridgehead carbon atom.
• the remaining carbon atoms available to accept substituents are indicated by numbers 1-4 on one phenyl group of the ligand, and numbers 5-8 on the other phenyl group of the fluorenyl ligand.
• the Fl group is unsubstituted, alternatively the Fl group is substituted.
• the Fl group may have any number and/or placement of substituent groups capable of producing the desired polymer product.
• the substituents on the Fl may comprise an aliphatic group; an aromatic group; a cyclic group; any combination thereof; any substituted derivative thereof, including but not limited to, a halide, an alkoxide, or an amide-substituted derivative thereof; any one of which has from 1 to 20 carbon atoms; or hydrogen.
• aliphatic groups include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each instance having from one to 20 carbon atoms.
• aliphatic groups include, but are not limited to, hydrocarbyls such as paraffins and alkenyls.
• Fl substituent groups may be the same or different and may include hydrogen radicals, alkyls (e.g.
• the Fl group is symmetrically disubstituted in the 3,6 positions, alternatively in the 2,7 positions.
• the substituents may be an alkyl group, an aryl group or combinations thereof.
• the Fl group is disubstituted at positions 3 and 6 with tert-butyl groups.
• the Fl group is disubstituted at positions 2 and 7 with tert-butyl groups.
• a catalyst for the polymerization of olefins comprises a ligand (Y) which may be represented by chemical formula (II) below:
• B is a bridging group that may be characterized by the general formula -YRH wherein Y comprises C or Si and R comprises an alkyl group, an aryl group, a poly-aryl group or combinations thereof.
• R is a poly-aryl group comprising at least two aryl groups, alternatively R is one of the compounds characterized by the chemical structures given in Group 1.
• a FMC for the polymerization of olefins comprises a metal (M).
• the metal atom "M" of the FMC may comprise atoms of Groups 3 through 12 and lanthanide Group atoms, alternatively atoms of Groups 3 through 10 , alternatively Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir or Ni.
• M comprises zirconium, hafnium, or titanium.
• M comprises zirconium.
• the oxidation state of the metal atom "M" may range from 0 to +7 or is
• a catalyst system for the polymerization of olefins comprises a FMC.
• the FMC may comprise a Cp group, a Fl group, a bridging group and a metal.
• the Cp group, Fl group, bridging group and metal may be of the type disclosed herein and may form a complex represented by the general chemical formula
• R' may comprise a C 1 - C 4 alkyl group, an aryl group, or combinations thereof and n' may range from 1 to 4.
• M may be titanium, zirconium or hafnium.
• Q may be a halogen, alkyl group, aryl group or combination thereof and R 3 and R 4 may be the same or different and each may be hydrogen, a methyl group, an isopropyl group, a tertiary butyl group, a phenyl group, a substituted phenyl group or combinations thereof.
• R 5 may be hydrogen, an alkyl group, an aromatic group or combinations thereof.
• R represents the remainder of the bridging group and may be an alkyl group, an aryl group, a poly-aryl group or combinations thereof.
• R is a poly-aryl group comprising at least two aryl groups, alternatively R is one of the compounds represented by the chemical structures given in Group 1.
• a FMC for the polymerization of olefins may be a zirconium metallocene complex represented by the chemical formulas IV-IX given in Table 1 wherein R and R' may be as described for formula III.
• the FMCs of this disclosure may be supported or unsupported.
• Typical support materials may include talc, inorganic oxides, clays and clay minerals, ion- exchanged layered compounds, diatomaceous earth compounds, zeolites or a resinous support material, such as a polyolef ⁇ n, for example.
• Specific inorganic oxides include without limitation silica, alumina, magnesia, titania and zirconia, for example.
• the inorganic oxides used as support materials may have an average particle size of from 30 microns to 600 microns or from 30 microns to 100 microns, a surface area of from 50 m 2 /g to 1,000 m 2 /g or from 100 m 2 /g to 400 m 2 /g and a pore volume of from 0.5cc/g to 3.5 cc/g or from 0.5 cc/g to 2 cc/g, for example.
• the synthesis of catalysts of the type disclosed herein may be carried out by any means known to one of ordinary skill in the art.
• the catalysts may be synthesized according to a methodology comprising fulvene preparation, bridging ligand preparation and metallation, as shown in Scheme I.
• the first step in the scheme involves fulvene synthesis.
• Fulvene synthesis is a base-catalyzed condensation of cyclopentadienes (or their derivatives) with aldehydes and ketones.
• the basic condensation agent may be an alkali metalhydrohide, an alkoxide, or an amine, and serves both to form the cylopentadienide ion, which effects nucleophilic attack of the carbonyl atom and to catalyze the dehydration of the intermediate as shown in Scheme II.
• the yield of fulvene synthesis depends on many factors including the reaction conditions, for example the reaction yield may vary depending on the type and concentration of the base used or on the reaction temperature.
• Some side reactions can occur during a fulvene formation, which decrease a yield of final product and require additional purification steps.
• One such side product is fulvene-methanol, the formation of which is depicted in Scheme III:
• the cyclopentadienes, and aldehydes/ketones exert steric and electronic effects that are influential on the product yield in fulvene formation reactions.
• a general rule of nucleophilic addition to carbonyl groups is that electron donating groups, which may be the substituents designated by R' and R' ' in Scheme III, increase the reaction rate when compared to a reaction carried out with electron withdrawing groups as the substitutents.
• the reaction of the base with an aldehyde may proceed faster than the reaction of a base with a ketone based on steric factors. Consequently, bulky substituents on cyclopentadienes (especially, at alpha carbons adjacent to methylene carbons) may dramatically decrease or altogether abolish the ability to form a fulvene, Scheme IV.
• the catalyst synthesis may begin with the formation of a fulvene such as for example, 6-(l-Naphthyl)-3-tert-butyl-5methyl-fulvene and related fulvenes.
• a fulvene such as for example, 6-(l-Naphthyl)-3-tert-butyl-5methyl-fulvene and related fulvenes.
• One method for the synthesis of a fulvene involves for example the reaction of methyl-tert-butyl-cyclopentadiene with acetone in methanol solution in the presence of pyrrolidine. The reaction may result in 6,6-dimethyl-methyl-butyl- fulvene with 50% yield and take several days for the reaction to occur. This reaction is depicted in Scheme V.
• an aryl substituted fulvene may be prepared by the reaction of a strong base such as sodium methoxide as shown in Scheme VI.
• the fulvenes may be produced by a phase transfer reaction
• PTR PTR
• Scheme VII the reaction of tert-butyl-cyclopentadiene with acetone in presence of NaOH and Bu 4 NBr as a PTR catalyst results in the corresponding fulvene with a yield of 95%.
• fulvene preparation methodologies disclosed herein using sodium methoxide as a base can be applied for synthesis of different fulvenes.
• Aryl 4-t-Bu-Ph, 4-Biphenyl 90%
• the process for the preparation of a polymerization catalyst of the type disclosed herein can be exemplified by the preparation of the FMC (l-naphthyl)[(3- Butyl-5 -methyl-cyclopentadienyl)(3 ,6-di-tert-butyl-fluorenyl)]methane zirconium dichloride using the three step process outlined in RXNs 1-3.
• bridging ligand was accomplished by reaction of lithium salt of 3,6-di-t-butyl-fluorene with 6-(l-Naphthyl)-3-tert-butyl-5-methyl-fulvene in ether solution, RXN 2. Specifically, treatment of the fluorenyl group with butyllithium results in an intermediate wherein the Li is substituted at position 9 of the fluorenyl group which then reacts further to substitute the fulvene at that position and form the bridged ligand.
• the complex is metallated, RXN 3, by double deprotonation of the ligand with 2 equiv of n-butyllithium in ether and subsequent reaction of the dilithium salt with ZrCl 4 in toluene affording the FMC, (l-naphthyl)[(3-Butyl-5-methyl- cyclopentadienyl)(3 ,6-di-tert-butyl-fluorenyl)]methane zirconium dichloride.
• the preparation of a fulvene as disclosed herein may result in a yield of from 60% to 99%, alternatively of from 70% to 95%, alternatively of from 80% to 95%.
• the formation of a bridged Cp and Fl group through the methodology disclosed herein may result in a yield of from 50% to 95%, alternatively of from 60% to 90%, alternatively of from 60% to 95%.
• the formation of a FMC of the type disclosed herein through metallation of a bridged Cp, Fl ligand may result in a yield of from 60% to 90%, alternatively of from 50% to 90%, alternatively of from 40% to 90%.
• the ligands produced by reactions according to the present disclosure are prepared by means of a very simple and efficient process, which employs inexpensive starting materials and comprises single reaction steps having high yield. Furthermore, this process does not require laborious and time-consuming purification procedures, and thus is particularly suitable to large-scale production.
• a catalyst system for the polymerization of olefins comprises a cocatalyst.
• the catalyst components of the present disclosure i.e. FMCs
• FMCs catalyst components of the present disclosure
• Suitable activating co-catalysts may take the form of co-catalysts that are commonly employed in metallocene-catalyzed polymerization reactions.
• the activating co-catalyst may take the form of an aluminum co-catalyst such as for example and without limitation alumoxane co-catalysts.
• Alumoxane co-catalysts are also referred to as aluminoxane or polyhydrocarbyl aluminum oxides.
• Such compounds include oligomeric or polymeric compounds having repeating units as indicated by the chemical formula shown in the formula X: R
• Alumoxanes are well known in the art and are generally prepared by reacting an organo-aluminum compound with water, although other synthetic routes are known to those skilled in the art. Alumoxanes may be either linear polymers or they may be cyclic, as disclosed for example in U.S. Pat. No. 4,404,344. Thus, alumoxane is an oligomeric or polymeric aluminum oxy compound containing chains of alternating aluminum and oxygen atoms whereby the aluminum carries a substituent, such as an alkyl group.
• linear and cyclic alumoxanes is generally believed to be represented by the general formula -(A1(R)-O) m for a cyclic alumoxane, and R 2 Al-O-(Al(R)-O) n J-AlR 2 for a linear compound wherein each R may independently comprise a C 1 -C 10 hydrocarbyl, alternatively, an alkyl group, a halide or combinations thereof and m is an integer ranging from 1 to 50, alternatively m is 4.
• Alumoxanes also exist in the configuration of cage or cluster compounds.
• Alumoxanes are typically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group may contain halide or alkoxide groups. Reacting several different aluminum alkyl compounds, such as, for example, trimethylaluminum and tri-isobutylaluminum, with water yields so-called modified or mixed alumoxanes. Examples of alumoxanes suitable for use in this disclosure are methylalumoxane and methylalumoxane modified with minor amounts of other higher alkyl groups such as isobutyl. Alumoxanes generally contain minor to substantial amounts of the starting aluminum alkyl compounds.
• the co-catalyst comprises poly (methylaluminum oxide), which may be prepared either from trimethylaluminum or tri-isobutylaluminum.
• Poly (methylaluminum oxide) may also be referred to as poly (isobutylaluminum oxide).
• the alkyl alumoxane co-catalyst and transition FMC are employed in any suitable amounts to provide an olefin polymerization catalyst.
• Suitable aluminum: FMC mole ratios are within the range of 10:1 to 20,000:1 alternatively, within the range of 50:1 to 10,000:1, alternatively, within the range of 100:1 to 5,000:1.
• the FMC component and the alumoxane, or other activating co-catalyst as described below are mixed prior to introduction in the polymerization reactor in a mode of operation such as described in U.S. Pat. No. 4,767,735 which is incorporated by reference herein in its entirety.
• activating co-catalysts which can be used include those catalysts which function to form a catalyst cation with an anion comprising one or more boron atoms.
• the activating co-catalyst may take the form of triphenylcarbenium tetrakis(pentafluorophenyl) boronate as disclosed in U.S. Pat. No. 5,155,080. As described there, the activating co-catalyst produces an anion which functions as a stabilizing anion in a transition metal catalyst system.
• Suitable noncoordinating anions include [W(PhF 5 )] ,[Mo(PhF 5 )] (wherein PhF 5 is pentafiuorophenyl), [ClO 4 ] “ , [S 2 O 6 ] “ , [PF 6 ] “ , [Sb ⁇ ' and/or, [AlR 4 ] " (wherein each R is independently C 1 , a Ci - C 5 alkyl group such as a methyl group, an aryl group, e.g. a phenyl or substituted phenyl group, a fluorinated aryl group or combinations thereof).
• activating co-catalysts For a further description of such activating co-catalysts, reference is made to the aforementioned U.S. Pat. No. 5,155,080, the entire disclosure of which was previously incorporated herein.
• activating co-catalysts which are suitable for use in the present disclosure include those catalysts which are supported on fluorinated silica supports. Such catalysts may contain MAO, alternatively such catalysts may not contain MAO.
• the polymerization reaction may be carried out in the presence of a scavenging agent or polymerization co- catalyst which is added to the polymerization reactor along with the catalyst component and activating co-catalyst.
• a scavenging agent or polymerization co- catalyst which is added to the polymerization reactor along with the catalyst component and activating co-catalyst.
• These scavengers can be generally characterized as organometallic compounds of metals of Groups IA, 2A, and 3B of the Periodic Table of Elements.
• organoaluminum compounds are normally used as co-catalysts in polymerization reactions.
• the activators may or may not be associated with or bound to a support, either in association with the catalyst (e.g, FMC) or separate from the catalyst component, such as described by Gregory G.
• catalyst systems comprising an FMC of the type disclosed herein may be used to catalyze the polymerization of alpha olefins.
• the catalyst system is prepared, as described above and/or as known to one skilled in the art, a variety of processes may be carried out using the catalyst system.
• the equipment, process conditions, reactants, additives and other materials used in polymerization processes will vary in a given process, depending on the desired composition and properties of the polymer being formed.
• the processes described above generally include polymerizing olefin monomers.
• the olefin monomers may include C 2 to C30 olefin monomers, or C 2 to Ci 2 olefin monomers (e.g., ethylene, propylene, butene, pentene, methylpentene, hexene, octene and decene), for example.
• Other monomers include ethylenically unsaturated monomers, C 4 to C 18 diolefins, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins, for example.
• Non-limiting examples of other monomers may include norbornene, nobornadiene, isobutylene, isoprene, vinylbenzocyclobutane, sytrene, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene, for example.
• the formed polymer may include homopolymers, copolymers or terpolymers, for example.
• the olefin polymerization may be carried out using solution phase, gas phase, slurry phase, bulk phase, high pressure processes or combinations thereof, for example. See, for example, U.S. Pat. Nos.
• One example of a gas phase polymerization process includes a continuous cycle system, wherein a cycling gas stream (otherwise known as a recycle stream or fluidizing medium) is heated in a reactor by heat of polymerization. The heat is removed from the cycling gas stream in another part of the cycle by a cooling system external to the reactor.
• the cycling gas stream containing one or more monomers may be continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The cycling gas stream is generally withdrawn from the fluidized bed and recycled back into the reactor.
• polymer product may be withdrawn from the reactor and fresh monomer may be added to replace the polymerized monomer.
• the reactor pressure in a gas phase process may vary from 100 psig to 500 psig, or from 200 psig to 400 psig or from 250 psig to 350 psig, for example.
• the reactor temperature in a gas phase process may vary from 30 0 C to 120 0 C, or from 60 0 C to 115 0 C, or from 70 0 C to 110 0 C or from 70 0 C to 95 0 C, for example. See, for example, U.S. Pat. Nos.
• Slurry phase processes generally include forming a suspension of solid, particulate polymer in a liquid polymerization medium, to which monomers and optionally hydrogen, along with catalyst, are added.
• the suspension (which may include diluents) may be intermittently or continuously removed from the reactor where the volatile components can be separated from the polymer and recycled, optionally after a distillation, to the reactor.
• the liquefied diluent employed in the polymerization medium may include a C 3 to C 7 alkane (e.g., hexane or isobutene), for example.
• the medium employed is generally liquid under the conditions of polymerization and relatively inert.
• a bulk phase process is similar to that of a slurry process. However, a process may be a bulk process, a slurry process or a bulk slurry process, for example.
• hydrogen may be added to the process for a variety of reasons. For example, hydrogen may be added to increase the melt flow of the resultant polymer, to increase the catalyst activity or, for molecular weight control of the resultant polymer. In an embodiment, hydrogen may be present in the reaction mixture in an amount of from 0 to 400 ppm, alternatively from 5 ppm to 200 ppm, alternatively from 10 ppm to 150 ppm.
• the polymerization carried out is a copolymerization of alpha-olef ⁇ n monomers.
• the polymerization process is copolymerization of ethylene with a second alpha-olef ⁇ n monomer.
• ethylene may be present in the feed in an amount of from 0 to 90 wt.%, alternatively from 0.5 wt.% to 50 wt.%, alternatively from 0.5 wt.% to 10 wt.%.
• a slurry process or a bulk process may be carried out continuously in one or more loop reactors.
• the catalyst as slurry or as a dry free flowing powder, may be injected regularly to the reactor loop, which can itself be filled with circulating slurry of growing polymer particles in a diluent, for example.
• the loop reactor may be maintained at a pressure of from 27 bar to 45 bar and a temperature of from 38 0 C to 121 0 C, for example.
• Reaction heat may be removed through the loop wall via any method known to one skilled in the art, such as via a double-jacketed pipe.
• the FMCs and catalyst systems comprising the FMCs disclosed are employed in the production of stereoregular polymeric compositions having a desired combination of physical properties such as molecular weight, melting temperature and tacticity.
• the FMCs and catalyst systems comprising an FMC of this disclosure are used in the production of copolymers of propylene with another alpha-olef ⁇ n.
• the catalysts and catalyst systems of this disclosure are used in the production of isotactic propylene.
• the isotactic polypropylene may have a molecular weight of less than 100,000 Daltons, alternatively from 100,000 to 1,000,000 Daltons, alternatively of from 200,000 to 800,000 Daltons.
• the isotactic polypropylene may have a melting temperature of from 120 0 C to 161 0 C, alternatively from 120 0 C to 145 0 C, alternatively from 159 0 C to 161 0 C.
• the isotactic polypropylene produced by the catalyst of this disclosure may be further characterized by a high tacticity ranging from 97% to 99% mmmm, alternatively from 96% to 99%, alternatively from 95% to 99%.
• the catalysts and catalyst systems of this disclosure are used in the production of copolymers of ethylene with another alpha-olefm monomer such as for example propylene.
• the percentage ethylene in the copolymer product may range from 0 to 80 wt.%, alternatively from 0.5 wt.% to 50 wt.%, alternatively from 0.5 wt.% to 30 wt.%.
• the polymeric compositions produced using the catalysts or catalyst systems of this disclosure may be useful in applications known to one skilled in the art, such as forming operations (e.g., film, sheet, pipe and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding).
• Films include blown or cast films formed by co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, and membranes, for example, in food-contact and non-food contact application.
• Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments and geotextiles, for example.
• Extruded articles include medical tubing, wire and cable coatings, geomembranes and pond liners, for example.
• Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, for example.
• Catalyst systems comprising the FMCs of this disclosure may produce isotactic polypropylene with a desirable combination of physical properties.
• the isotactic polypropylene may be characterized by a molecular weight of from 400,000 to 1,000,000 Daltons, a melting temperature of from 159 0 C to 161 0 C and a tacticity of from 97% to 99% mmrnm.
• Catalysts useful for the production of isotactic polypropylene of this type may be characterized by the general formula XI:
• R' comprises H or Me and R comprises Me or a compound selected from the following group:
• the isotactic polypropylene produced using the catalyst systems comprising the FMCs of this disclosure may be characterized by a molecular weight of from 100,000 to 1,000,000 Daltons and a melting temperature of from 120 0 C to 145 0 C.
• Catalysts useful for the production of isotactic polypropylene of this type may be characterized by the general formula XII:
• R' comprises H or Me and R comprises Me or a compound selected from the following group:
• the isotactic polypropylene produced using the catalyst systems comprising the FMCs of this disclosure may be characterized by a molecular weight of less than 100,000 Daltons and a melting temperature of from 120 0 C to 145 0 C.
• Catalysts useful for the production of isotactic polypropylene of this type may be characterized by the general formula XIII:
• R' comprises H or Me and R comprises Me or a compound selected from the following group: ,
• the catalysts of the present disclosure can be advantageously used in propylene polymerization to produce isotactic polypropylenes having a desired combination of physical properties. Desired features of the catalysts of the present disclosure are due to a unique combination of structural parameters of the catalysts and substitutions of the cyclopentadienyl and fluorenyl rings.
• the catalysts of the present disclosure can be used in copolymerization of propylene with olefins, e.g. ethylene to yield random or impact copolymers with low melt flow rates.
• Catalyst A (fluorenyl)] methane zirconium dichloride, hereafter referred to as Catalyst A.
• the synthesis began with preparation of a fulvene, 6-(l-Naphthyl)-5- methyl-3-tert-butyl-fulvene as follows: to a solution of methyl-tert- butylcyclopentadiene (4.35g, 32.0 mmol) and 1-naphthaldehyde (5.Og, 32.0 mmol)) in absolute ethanol (50 ml) was added a small portion of sodium methoxide (4.5 g) under stirring and the mixture was stirred for Ih. The reaction was quenched with water and extracted with ether.
• the 1 H NMR was run in CDCI3 and the chemical shifts are as follows: ⁇ 7.98, 7.95 (s, IH, Naph), 7.15 and 7.13 (s, IH, Naph), 7.8, 7.7 and 7.5 (m, Naph + H), 6.22 and 6.21 (br s, 2H, H-Cp), 2.18 and 2.15 (s, 3H, Me), 1.20 and 1.17 (s, 9H, t-Bu).
• the synthesis proceeded with the formation of the bridged Fl-Cp ligand: (2-Naphthyl)-[(5-methyl-3-tert-butyl)3,6-di-tert-butyl- (fluorenyl)]methane.
• Butyllithium (2.8 ml, 1.6M in hexane, 4.48 mmol) was added to 3,6-di-t-butyl-fluorene (1.20 g, 4.35 mmol) in ether (20 ml) at -78 0 C. The reaction mixture was allowed to warm to room temperature and stirred for 4h. 6-(2-Naphthyl)-5- methyl-3-tert-butyl-fulvene (1.19 g, 4.34 mmol) in ether (10 ml) was added to the reaction mixture at -40 0 C. The reaction was stirred at room temperature for 1.5h.
• the reaction mixture was quenched with water, extracted with ether, dried over MgSO 4 , and evaporated under vacuum to afford the desired ligand.
• the metallated catalyst (2-Naphthyl)-[(5-methyl-3-tert-butyl)3,6-di-tert- butyl-(fluorenyl)]methane zirconium dichloride was prepared.
• Butyllithium (2.5 ml, 1.6M, 4.0 mmol) was added to (2-naphthyl)-[(5-methyl-3-tert-butyl)3,6-di-tert-butyl- (fluorenyl)]methane (1.06g, 1.93 mmol) in ether (20 ml) at -78 0 C.
• the reaction mixture was allowed to heat to room temperature and the reaction was continued for 3h.
• the solvent was removed under vacuum.
• ZrCl 4 (460mg, 1.97 mmol) was added to the reaction mixture.
• Toluene (15 ml) was added at -40 0 C and the reaction was stirred at room temperature overnight. Herein, overnight refers to time period equal to or greater than 8 hours.
• the solvent was removed under vacuum.
• Example 1 are characterized by having a napthyl group as the bridging ligand, a symmetric 3,6 tert-butyl substitution of the fluorenyl group and a 5 -methyl, 3-tert-butyl substitution of the cyclopentadienyl group.
• the general formulas of these catalysts are given below in Structures XIV and XV for Catalysts A and B respectively.
• Multi-Clave reactor at 20 and 60 0 C using Catalysts A-C without purification The reactions were run for 30 minutes in the absence of hydrogen with a FMC/MAO of 1/1000.
• the results in terms of polymerization parameters and polymer properties are given in Table 2.
• Catalyst A produced polymers with melting points of 161 and 159 0 C at polymerization temperatures of 20 and 60 0 C respectively.
• Catalyst A and B were supported on silica supports available from Asahi Glass Co., Ltd. under the designation G-952.
• G-952 silica with 2 wt% loading of the Catalyst A or Catalyst B were tested in a 6-parallel
• the 13 C NMR indicates that copolymer produced by Catalyst A is dramatically enriched in ethylene compared to the feed composition.
• the EPE triad is more enriched than would be predicted from truly random copolymerization, therefore, Catalyst A has a tendency towards alternating copolymerization between ethylene and propylene.
• the catalyst structure is depicted in Structure XVII.
• the polymerization of propylene was carried out as described in Example 2 and the results of the polymerization are presented in Table 8.
• Catalyst D The activity of Catalyst D is considerably higher than that observed with the Catalysts A or B (see Table 3) and is similar to that observed with the Catalyst C used for comparison. Furthermore, polypropylene resins produced using Catalyst D exhibit a moderate melting temperature, 154.0 0 C, with a moderate average molecular weight of 507,800 Daltons.
• a catalyst containing a mono-phenyl tert-butyl group as the bridging ligand was prepared, Catalyst E.
• the structure of the catalyst employed is shown as Structure XVIII.
• Catalyst E was synthesized using the general methodology described in
• Example 1 Specfically, synthesis of 6-(4-t-Butyl-phenyl)-5-methyl-3-tert-butyl- fulvene was carried out as follows: to a solution of methyl-tert-butylcyclopentadiene (4.42g, 32.5 mmol) and 4-t-butyl-benzaldehyde (5.15g, 31.8 mmol) in absolute ethanol (50 ml) was added a small portion of sodium methoxide (4.5 g) under stirring and the mixture was stirred for 2h. The reaction was quenched with water and extracted with ether.
• butyl-(fluorenyl)]methane zirconium dichloride was carried out as follows: Butyllithium (1.7 ml, 1.6M, 2.72 mmol) was added to (4-t-butyl)-[(5-methyl-3-tert-
• Catalyst E produced isotactic polypropylene with tacticity of 96% mmmm, Table 10, a melting temperature of 166-167 0 C, Table 11, and molecular weight of 670,000. The activity of 74,000 g/gCat/h was observed under an initial hydrogen concentration of 20 ppm. Table 10
• the supported catalyst produced highly isotactic polypropylene with tacticity of 97% mmmm and melting temperature of 156-157 0 C.
• the molecular weight of polymers, produced by Catalyst G/G-952 depends on hydrogen concentrations and is in a range of 370,000-200,000 for polymerization at 88-100 ppm of H 2 as shown in Figures 3 and 4 respectively.
• the activity of the catalyst was 600 g/g/cat at 88 ppm of H 2 , shown in Figure 5.
• Catalyst B and Catalyst C was made for homo propylene polymerization to produce isotactic polypropylene (iPP) at 6O 0 C and 60-70 ppm of H 2 concentration.
• the melting temperatures of iPP produced with Catalyst E were 156.4 0 C. This is close to the melting temperatures of iPP from Catalyst G and higher when compared with Catalyst C iPP (143 0 C), Figure 9.
• Catalyst G is characterized by a 3,6 symmetrically substituted Fl group, an unsubstituted Cp group and a napthyl bridging group.
• the tacticity of all catalysts having a 3,6-fluorenyl substitutent is 96-97% mmmm.
• the molecular weight comparison for iPP produced at 60 ppm of H 2 shows that Catalyst E produces the highest molecular weight iPP (267,700) when compared with catalysts of the type exemplified by Catalyst A (194,000), Catalyst G (93,000) and Catalyst C (181,000).
• the activity of Catalyst E was 600 g/gCat/h (at 88 ppm OfH 2 ) which was lower than for Catalysts A-C.
• the molecular weight of random copolymers produced with Catalyst A decreases with increasing ethylene content in feed which is similar to catalysts Catalysts G and C, see Table 15 and Figure 10.
• Catalyst E also produces a higher melting temperature RCP than Catalyst A and Catalyst C with the same ethylene content, see Figure 12.
• a catalyst having a biphenyl substituted bridging ligand was synthesized.
• (biphenyl)-[(5-methyl-3-tert-butyl)3,6-di-tert-butyl-(fluorenyl)]methane was synthesized by adding Butyllithium (3.8 ml, 1.6M in hexane, 6.08 mmol) to 3,6- di-t-butyl-fluorene (1.62 g, 5.87 mmol) in ether (20 ml) at -78 0 C. The reaction mixture was allowed to warm to room temperature and stirred for 5 h.
• Catalysts useful in the production of isotactic polypropylene with a high molecular weight and a moderate melting temperature were synthesized.
• Catalysts H and I are characterized by a napthyl group as the bridging ligand, a symmetric 2,7 tert- butyl substitution of the fluorenyl group and a 5-methyl, 3-tert-butyl substitution of the cyclopentadienyl group.
• the structures of Catalysts H and I are given below by Structures XIX and XX respectively.
• the polymerization of propylene was carried out as described in Example 2 using these catalysts supported on G-952 silica in a parallel six-reactor set.
• Table 17 presents the results in terms of polymerization parameters and polymer properties for Catalysts H and I supported on G-952 silica which can be compared to the results observed with the use of Catalyst A under similar conditions given in Table 18.
• Catalyst H increases with increasing ethylene concentration in feed under the same concentration of hydrogen.
• the activity of 1,100 g/gCat/h was observed under the initial hydrogen concentration of 60 ppm and ethylene concentration of 1.0 wt%, see Figure 13.
• the molecular weight slightly decreased with increasing ethylene content under the same initial hydrogen concentration, see Figure 14.
• Catalyst H produced copolymers with melt flows under 15 g/10 min with ethylene contents of up to 3.0 wt% and melting points higher than 111 0 C under polymerization with hydrogen concentration less than 40 ppm, see Figure 15.
• the percent of xylene soluble fraction of homopolymer is less than 1% and dramatically increased with increasing ethylene content in copolymer higher than 1.5-2.0%, see Figure 16.
• Catalyst J the structure of which is shown in Structure XXI and the results of the copolymerization of ethylene and propylene in terms of polymerization activity of Catalyst J and polymer properties is given in Table 21.
• Catalysts useful in the production of isotactic polypropylene with a high to moderate molecular weight and a low melting temperature were synthesized. These catalysts exemplified by Catalyst K are characterized by a napthyl group as the bridging ligand, an unsubstituted fluorenyl group and a 5 -methyl, 3-tert-butyl substitution of the cyclopentadienyl group. Catalyst K was prepared as follows:
• the ligand was purified by column chromatography (SiO 2 , hexanes/methylene chloride (3.8g, 75%).
• the 1 H NMR in CDCl 3 was carried out and the chemical shift data is as follows: ⁇ 8.1-6.6 (m, Flu, Naphth), 6.11 and 5.91 (s, IH, H-Cp), 4.8 (m, 2H, H9-Flu and H-bridge), 2.8 (several br s, 2H, CH2-Cp), 1.69 and 1.65 (s, 3H, Me), 1.16 and 1.13 (s, 2.31 (s, 3H, Me), 1.23 (s, 9H, t-Bu).
• Catalyst K produced a polymer with a melting point of 131 0 C and a molecular weight of 333,000.
• Catalyst K was supported on G-952 silica with 2 wt% loading and tested in the 6-parallel reaction set. Polymerization data for Catalyst J/G-952 is shown in Table 23.
• the catalyst produced polymers with melting temperatures in the range of 132-142 0 C under polymerization at 60 0 C and hydrogen concentrations of 0-60 ppm.
• the melting point of the polymer is observed to increase with increasing a hydrogen concentration, see Figure 17.
• the melt flow rate appears to plateau with increasing hydrogen concentration, see Figure 18 while the molecular weight decreases with increasing hydrogen concentration as shown in Table 23.
• the polymer produced had a melt flow rate of 16 g/10 min.
• the observed activity at this condition was around 1,300 g/gCat/h.
• the catalyst produced isotactic polypropylene with % mmmrn of 80-83 as shown in Table 24.
• the FMC (4-Biphenyl)-[(5-methyl-3- tert-butyl-cyclopentadienyl) (fluorenyl)]methane zirconium dichloride was prepared. Specifically, butyllithium (3.3 ml, 1.6M, 5.28 mmol) was added to (4-biphenyl)-[(5- methyl-3-tert-butyl)(fluorenyl)]methane (1.17g, 2.51 mmol) in ether (20 ml) at -78 0 C. The reaction mixture was allowed to heat to room temperature and the reaction was continued overnight. The solvent was removed under vacuum.

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