WO2006137818A1 - Composants de catalyseur et leur utilisation dans la polymerisation d'olefines - Google Patents

Composants de catalyseur et leur utilisation dans la polymerisation d'olefines Download PDF

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WO2006137818A1
WO2006137818A1 PCT/US2005/000109 US2005000109W WO2006137818A1 WO 2006137818 A1 WO2006137818 A1 WO 2006137818A1 US 2005000109 W US2005000109 W US 2005000109W WO 2006137818 A1 WO2006137818 A1 WO 2006137818A1
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group
substituted
phenyl
catalyst
alkyl
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PCT/US2005/000109
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English (en)
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Vlaimir Marin
Abbas Razavi
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Fina Technology, Inc.
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Priority to PCT/US2005/000109 priority Critical patent/WO2006137818A1/fr
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    • 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
    • C07F17/00—Metallocenes
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • 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

Definitions

  • This invention relates to olefin polymerization catalysts and their use in the polymerization of ethylenically unsaturated monomers.
  • Olefin polymers such as polyethylene, polypropylene, which may be atactic or stereospecific, such as isotactic or syndiotactic, and ethylene-higher alpha olefin copolymers, such as ethylene-propylene copolymers can be produced under various polymerization conditions and employing various polymerization catalysts.
  • Such polymerization catalysts include Ziegler-Natta catalysts and non-Ziegler-Natta catalysts, such as metallocenes and other transition metal catalysts which are typically employed in conjunction with one or more co- catalysts.
  • the polymerization catalysts may be supported or unsupported.
  • the alpha olefin homopolymers or copolymers may be produced under various conditions in polymerization reactors which may be batch type reactors or continuous reactors.
  • Continuous polymerization reactors typically take the form of loop-type reactors in which the monomer stream is continuously introduced and a polymer product is continuously withdrawn.
  • polymers such as polypropylene, polyethylene or ethylene-propylene copolymers involve the introduction of the monomer stream into the continuous loop-type reactor along with an appropriate catalyst system to produce the desired olefin homopolymer or copolymer.
  • the resulting polymer is withdrawn from the loop-type reactor in the form of a "fluff which is then processed to produce the polymer as a raw material in particulate form as
  • the resulting polymer product may be characterized in terms of stereoregularity, such as in the case of, for example, isotactic polypropylene or syndiotactic polypropylene.
  • isotactic polypropylene can be described as one having the methyl groups attached to the tertiary carbon atoms of successive monomelic units falling on the same side of a hypothetical plane through the main chain of the polymer, e.g., the methyl groups are all above or below the plane.
  • the stereochemical sequence of isotactic polypropylene is described as follows:
  • each vertical segment indicates a methyl group on the same side of the polymer backbone.
  • Another way of describing the structure is through the use of NMR. Bovey's NMR nomenclature for an isotactic pentad as shown above is ...mrnrnm... with each "m” representing a "meso" dyad, or successive pairs of methyl groups on the same said of the plane of the polymer chain. As is known in the art, any deviation or inversion in the structure of the chain lowers the degree of isotacticity and crystallinity of the polymer.
  • syndiotactic propylene polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomelic units in the chain lie on alternate sides of the plane of the polymer.
  • Syndiotactic polypropylene using the Fisher projection formula can be indicated by racemic dyads with the syndiotactic pentad rrrr shown as follows:
  • the vertical segments again indicate methyl groups in the case of syndiotactic polypropylene, or other terminal groups, e.g. chloride, in the case of syndiotactic polyvinyl chloride, or phenyl groups in the case of syndiotactic polystyrene.
  • Other unsaturated hydrocarbons which can be polymerized or copolymerized with relatively short chain alpha olefins, such as ethylene and propylene include dienes, such as 1,3-butadiene or 1,4-hexadiene or acetylenically unsaturated compounds, such as methylacetylene.
  • a particularly preferred application of the invention is in the polymerization of propylene including the homopolymerization of propylene to produce polypropylene, preferably isotactic polypropylene,
  • copolymer specifically an ethylene-propylene copolymer.
  • an olefin polymerization catalyst characterized by the formula:
  • Flu is a fluorenyl group substituted at at least one of the 4 or 5 positions by a bulky hydrocarbyl group having at least 3 carbon atoms.
  • A is a substituted or unsubstituted cyclopentadienyl or indenyl group or a heteroorgano group, XR, in which X is a heteroatom from Group 15 or 16 of the Periodic Table of Elements, and R is an organo group.
  • X is nitrogen, phosphorus, oxygen or sulfur. More preferably, X will take the form of nitrogen.
  • R is an alkyl group or cycloalkyl group containing from 1 to 20 carbon atoms, or a mononuclear aromatic group which may be substituted or unsubstituted.
  • B is a structural bridge extending the groups A and Flu, which imparts stereorigidity to the ligand structure.
  • the bridge B is characterized by the formula ER 1 R", in which E is a carbon, silicon or germanium atom, and R' and R" are each independently an alkyl group, an aromatic group or a cycloalkyl group.
  • M is a Group 4 or Group 5 transition metal, preferably titanium, zirconium or hafnium.
  • Q is selected from the group consisting of chlorine, bromine, iodine, an alkyl group, an amino group, an aromatic group and mixtures thereof, n is 1 or 2 and will have a value of 2 where the transition metal is zirconium, hamium or titanium.
  • the fluorenyl group is substituted at both of the 4 or 5 positions with a bulky hydrocarbyl group containing at least 3 carbon atoms.
  • the bulky hydrocarbyl group may take the form of isopropyl groups or tetra-butyl groups or phenyl or substituted phenyl groups.
  • the group A is substituted or configured in order to provide asymmetry for the ligand structure extending through the bridge group and the transition metal atom.
  • A may take the form of an indenyl group which is substituted or unsubstituted, or a cyclopentadienyl group which is substituted at the 3 or the 3 and 5 positions.
  • the fluorenyl group is mono- substituted at the 4 (or 5) position and is otherwise unsubstituted or is di-substituted at the 2,7 positions with alkyl or phenyl or substituted phenyl groups.
  • the fluorenyl group is substituted at the 4(5) position with a bulky substituent, specifically an isopropyl or a tetra-butyl group or a substituted or unsubstituted phenyl group and di-substituted at the 2,7 positions with substituents.
  • the substituents at the 2,7 position are of a lower molecular weight than the substituent at the 4(5) position.
  • the fluorenyl group, in addition to substitution at the 2,7 positions is also di-substituted at the 3,6 position.
  • the substituents at the 3,6 position may be the same as the substituents at the 2,7 position, but normally will be of a lower molecular weight than the substituents at the 2,7 position.
  • the substituents at the 2,7 position are the same and the substituents at the 3,6 positions are the same.
  • the ligand component A is a cyclopentadienyl group substituted at the 3 position with a tertiary butyl group and the fluorenyl group is substituted at the 4(5) position with a substituted or unsubstituted phenyl group.
  • the cyclopentadienyl group is a also substituted at the 5 position with a methyl group.
  • the catalyst component is characterized by the formula:
  • R' is a Ci - C 4 alkyl group or an aryl group
  • R" is a methyl group and n' and n"
  • B is a structural bridge between the fluorenyl and cyclopentadienyl groups and M is titanium, zirconium or hamium.
  • Q is as characterized above
  • R 3 and R 4 are the same or different and are each a hydrogen or an
  • R 5 is an alkyl or
  • R 3 and R' 4 are each hydrogen
  • R 3 and R 4 are isopropyl or tertiary butyl groups, R 3 and R' 4 may also be isopropyl
  • R in formula (4) is
  • n' is 1
  • R 3 and R 4 are each isopropyl or tertiary butyl groups and R 5 is a
  • n is 1.
  • the cyclopentadienyl group is substituted at the 3 position with a tertiary butyl group and at the 5 position with a methyl
  • R 5 is preferably a 4-tertiary butyl phenyl group.
  • the olefin polymerization catalyst is characterized by the formula:
  • R is a mononuclear aromatic group or an alkyl group or cycloalkyl group containing from 1 to 20 carbon atoms.
  • B is a structural bridge between the fluorenyl group and the heteroatom group NR, and M, Q, R 3 and R 4 , R'3, R' 4 and R 5 are as defined above with
  • the olefin polymerization catalyst is characterized by the formula:
  • R' is a C 1 - C 4 alkyl group or an aryl group and n' is from 0 (resulting in an
  • R" is an alkyl group of lower molecular weight than R and n" is 0 or 1.
  • E is -C- or -Si- extending between the fluorenyl and cyclopentadienyl groups and Ri and R 2 are
  • M is a titanium, zirconium or hafnium atom
  • Q is a chlorine, methyl group or phenyl group.
  • R 3 and R 4 are the same or different are each a hydrogen or a Ci - C 4 alkyl group, phenyl or
  • R 5 is an alkyl group or an aromatic group which has a higher
  • R' 3 and R' 4 are the same or different and are a hydrogen or a Ci
  • R 3 and R 4 are alkyl groups
  • R' 3 and R' 4 may be hydrogen or alkyl groups with R' 3 and R' 4
  • R 5 is tertiary butyl group, a phenyl group or a 4-tertiary butyl group.
  • processes for the polymerization of one or more ethylenically unsaturated monomers to produce a corresponding homopolymer or copolymer there is provided a transition metal catalyst as characterized by the above formulas (3), (4), (5) and (6).
  • an activating co-catalyst component such as an alumoxane.
  • the catalyst component and the co-catalyst component are contacted in a polymerization reaction zone with an ethylenically unsaturated monomer under polymerization conditions to produce a polymer product which is then recovered from the reaction zone.
  • the activating co-catalyst comprises methylalumoxane (MAO) or tri-isobutylalumoxane (TIBAO) or mixtures thereof.
  • the activating co-catalyst can take the form of a noncoordinating anionic type, such as triphenylcarbenium tetrakis(pentafluorophenyl)aluminate or triphenylcarbenium
  • the ethylenically unsaturated monomer is a C 3+
  • alpha olefin More specifically, the alpha olefin is propylene and the polymerization reaction is carried out to produce isotactic polypropylene.
  • the present invention involves bridged transition metal catalysts having and their use in the polymerization of olefins.
  • olefins which may be polymerized, either through homopolymerization or copolymerization include ethylene, propylene, butylene, as well as monoaromatic or substituted vinyl compounds as described previously.
  • the bridged catalyst components of the present invention incorporate transition metals from Groups 4 or 5 of the Periodic Table of Elements (new notation) and more particularly, transition metals from Group 4 of the Periodic Table of Elements.
  • Preferred transition metals for use in the catalyst components of the present invention are titanium, zirconium and hafnium, with zirconium being particularly preferred.
  • catalyst components of the present invention incorporate substituted fluorenyl groups which are bridged to substituted or unsubstituted cyclopentadienyl or indenyl groups or heteroorgano groups and are substituted in a manner to provide ligand structures which are unbalanced with respect to a plane of symmetry through the bridge and the transition metal. More specifically, catalyst components of the present invention comprise metallocene ligand structures which incorporate substituted fluorenyl groups which are bridged to substituted or unsubstituted cyclopentadienyl or indenyl groups or heteroorgano groups and which are substituted in a manner in which the ligand structures are asymmetric with a plane of symmetry extending through the bridge and the transition metal.
  • Diagram (7) indicates a cyclopentadienyl-fluorenyl ligand structure, diagram (8 an indenyl-fluorenyl ligand structure and diagram (9) a heteroatom (XR)-fluorenyl ligand structure.
  • the numbering schemes used to indicate the position of substituents on the various ligand structures are indicated on diagrams (7), (8) and (9).
  • the indenyl moiety may take the form of 4,5,6,7-tetrahydro indenyl as well as the more common unhydrogenated indenyl group.
  • the metallocene ligand structures may be characterized in terms of a plane of symmetry extending perpendicular to the plane of the paper through the bridge group B and the transition metal (not shown) in diagrams (7), (8) and (9) which would project upwardly from the plane of the paper.
  • the cyclopentadienyl group may be unsubstituted and the fluorenyl group may be substituted at the 4 position with a relatively bulky isoalkyl group, specifically a tertiary butyl group, or a phenyl group which may be substituted or unsubstituted. If there are no other substituents or if the cyclopentadienyl group or fluorenyl group are otherwise symmetrically substituted, the 4 position is equivalent to the 5 position on the fluorenyl group and this relationship is expressed by the positional expression 4(5).
  • the present invention involves bridged transition metal catalysts having the fluorenyl ligand with bulkier substituent at least at the 4-(5-) fluorenyl position and their use in the polymerization of olefins.
  • the bulkier groups at the 4- and 5- positions of fluorenyl ligand described in the invention provide specific features of the catalysts, especially in alpha-olefin polymerization such as propylene polymerization.
  • the catalyst precursors of the present invention are represented by the formula:
  • fluorenyl ligand is substituted with at least one bulky group (at least three carbon
  • R' 5 is a bulky substituent. That is, the sterically hindering group
  • Non-limiting examples of fluorenyl ligands include:
  • R 3 , R 4 , R 5 , R 6 are each an alkyl or aryl.
  • the catalysts of the present invention can be advantageously used in propylene polymerization to produce isotactic polypropylene with high yield, having high molecular weight, high tacticity and high melt temperature. Desired features of the catalysts of the present invention are due to a unique combination of structure parameters of the catalysts, substitutes at the cyclopentadienyl and fluorenyl rings, and a presence of two stereoisomers, each of them produces isotactic polymers.
  • the catalysts of the present invention can be used in copolymerization of propylene with olefins, e.g. ethylene to yield random or impact copolymers.
  • Ligand structures suitable for use in carrying out the present invention which can be employed to produce isotactic polypropylene include, with reference to diagram (7), 3-tertiary butyl, 5-methyl cyclopentadienyl, 2,7-ditertiary butyl, 4-phenyl fluorene, the same ligand structure except with substitution on the fluorenyl structure at the 5 position and the same ligand structure with substitution at the 4 or 5 position by a 4-tertiary butyl phenyl group.
  • the phenyl group is substituted by a tertiary butyl group at the directly distal position with respect to the substitution of the phenyl group on the fluorenyl group.
  • Suitable ligand structures which can be employed to produce isotactic polypropylene include ligand structures such as described above, except the cyclopentadienyl group is mono-substituted at the 3 position with a tertiary butyl group.
  • the fluorenyl group is substituted as before at the 2 and 7 position with the tertiary butyl groups and at the 4 position with a phenyl group or a 4-tertiary butyl phenyl group.
  • substituted ligand structures may be employed in accordance with the present invention incorporate a bis-indenyl fluorenyl ligand structure exemplified by diagram (8).
  • the fluorenyl ligand component may be substituted as described previously, thus, it may be substituted at the 4 position or di-substituted at the 4 and 5 position with bulky groups, such as tertiary butyl and phenyl groups.
  • the fluorenyl ligand structure may be substituted at one of the 4 and 5 positions and di-substituted at the 2 and 7 positions with substituent groups, which are less bulky than the substituents on the 4 or 5 position.
  • the heteroatom ligand structure depicted in diagram (9) may be substituted on the fluorenyl group similarly as described above with respect to diagrams (7) and (8).
  • the fluorenyl group may be substituted at the 2 and 7 positions with tertiary butyl groups and substituted at the 4 position with a substituted or unsubstituted phenyl group.
  • the fluorenyl group may be unsubstituted at the 2 and 7 positions and substituted at the 4 position with an isopropyl group, a tert-butyl group, a phenyl group or a substituted phenyl group.
  • activating co-catalysts may take the form of co-catalysts such are commonly employed in metallocene-catalyzed polymerization reactions.
  • the activating co-catalyst may take the form of an aluminum co-catalyst.
  • Alumoxane co-catalysts are also referred to as aluminoxane or polyhydrocarbyl aluminum oxides.
  • Such compounds include oligomeric or polymeric compounds having repeating units of the formula:
  • 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. Patent 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, preferably an alkyl group.
  • the structure of linear and cyclic alumoxanes is generally believed to be represented by the general
  • R independently each occurrence is a Ci - Cio hydrocarbyl, preferably alkyl or
  • halide and m is an integer ranging from 1 to about 50, preferably at least about 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. Preferred alumoxanes 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 preferred co-catalyst prepared either from trimethylaluminum or tri-isobutylaluminum, is sometimes referred to as poly (methylaluminum oxide) and poly (isobutylaluminum oxide), respectively.
  • the alkyl alumoxane co-catalyst and transition metal catalyst component are employed in any suitable amounts to provide an olefin polymerization catalyst. Suitable aluminum transition metal mole ratios are within the range of 10:1 to 20,000:1 and preferably within the range of 100:1 to 5,000:1.
  • the transition metal catalyst 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. Patent No. 4,767,735 to Ewen et al.
  • the polymerization process may be carried out in either a batch-type, continuous or semi-continuous procedure, but preferably polymerization of the olefin monomer (or monomers) will be carried out in a loop type reactor of the type disclosed in the aforementioned patent no. 4,767,735.
  • Typical loop type reactors include single loop reactors or so-called double loop reactors in which the polymerization procedure is carried in two sequentially connected loop reactors.
  • the catalyst components when they are formulated together, they may be supplied to a linear tubular pre-polymerization reactor where they are contacted for a relatively short time with the pre-polymerization monomer (or monomers) prior to being introduced into the main loop type reactors.
  • Suitable contact times for mixtures of the various catalyst components prior to introduction into the main reactor may be within the range of a few seconds to 2 days.
  • activating co-catalysts which can be used in carrying out the invention 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. Patent No. 5,155,080 to Elder et al. 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(PhFs)] “ , [Mo(PhFs)] "” (wherein PhFs is pentafluorophenyl),
  • triphenylcarbenium tetrakis(pentafluorophenyl) boronate may be reacted with pyridinyl-linked bis-amino ligand of the present invention in a solvent, such as toluene, to produce a coordinating cationic-anionic complex.
  • a solvent such as toluene
  • 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.
  • Scavenging co-catalysts normally employed in the invention include methylalumoxane (MAO), triethylaluminum (TEAL) and tri-isobutylaluminum (TTOAL).
  • MAO methylalumoxane
  • TEAL triethylaluminum
  • TTOAL tri-isobutylaluminum
  • the bridged fluorenyl ligand structures and the corresponding transition metal catalyst components can be prepared by any suitable techniques.
  • the fluorenyl group is treated with methyl lithium to result in a fluorenyl group substituted with lithium in the 9 position and this is then reacted with a 6,6 substituted fulvene.
  • 6,6-dimethyl fulvene may be employed to produce the isopropylidene cyclopentadienyl substituted fluorenyl ligand structure.
  • the lithiumated fluorenyl group is reacted, for example, with diphenylsilyl dichloride to produce the diphenylsilyl chloride substiruent at the 9 position on the fluorenyl group.
  • This component is then reacted with the lithiumated cyclopentadienyl or substituted cyclopentadienyl to produce the bridge.
  • the ligand structure is then treated with methyl lithium, followed by reaction with the appropriate transition metal, chlorine, e.g. zirconium tetrachloride, to produce the corresponding metallocene dichloride.
  • R 3 and R 4 are the same and are hydrogen or a tert-butyl group and R 5 is a bulky alkyl
  • aryl group or an aryl group e.g. a phenyl group or a tertiary butyl phenyl group, may be generally characterized by the following sequence:
  • step one the fluorine reacts with 2,6-di-tertbutyl-4-methylphenol in the presence of aluminum chloride to give 2,7-di-tert-butyl-fluorene.
  • step two the 2,7-di-tert-butyl fluorene selectively reacts with bromine in the presence of an iron catalyst to produce 4-bromo-2,7-di-tert-butyl-fluorene.
  • step three of the method 4-bromo-2,7-di-tert-butyl-fluorene is reacted with aryl boronic acid in the presence of palladium catalyst to form 4-aryl-2,7-di-tert-butyl-fluorene.
  • 4-iodo-2,7-di-tert-butyl-fluorene is reacted with alkyl Grignard reagent to give corresponding 4-alkyl-2,7-di-tert-butyl-fluorene.
  • alkyl Grignard reagent A variety of aryl boronic acids and Grignard reagents allow the attachment of different substituents at the 4-position of fluorene.
  • step four the bridged ligand is synthesized by using 4-substituted fluorene.
  • the 4-substitued fluorene is deprotonated by reacting with it at least one equivalent of methyllithium or butyllithium. The resulting anion is reacted with fulvene to produce the bridged ligand.
  • the ligands produced by reactions according to the present invention are prepared by means of a very simple and efficient process, which employs inexpensive starting materials and comprises single reaction steps having high yields. Furthermore, this process does not require laborious and time-consuming purification procedures, and thus is particularly suitable to large-scale production.
  • Example 5 Synthesis of 4-f4-tert-Butylphenyiy2,7-di-t-butylfluorene [0045] To a mixture of 4-bromo-2,7-di-t-butylfluorene (1.34 g, 3.75 mmol) and Pd(PPh 3 ) 4 (300 mg, 0.26 mmol) in toluene (50 ml) was added a solution of 4-tert- butylphenylboronic acid (1.00 g, 5.62 mmol) in EtOH (10 ml) and a solution OfNa 2 CO 3 (1.19 g) in water (15 ml). The reaction mixture was stirred for 20 hours under reflux.
  • Example 9 [Cyclopentadienyi ⁇ 4-(4-tert-butyl)phenyl-2,7-di-tert- butylfluorenyDpropanelzirconium dichloride (Catalyst 2) [0049] The same procedure as in Example 7 was repeated except that reaction was conducted by using the ligand from Example 8.
  • Example 12 2.2-[(3-tert-butyl-5-methyl-cvclopentadienylV
  • Example 18 (3-tert-Butyl-5-methyl-cvclopentadienyl)-(4-phenyl-2J-di-tert- butylfluorenvDdimethvlsilane [0061] The same procedure as in Example 16 was repeated except that reaction was conducted by using the methyl-tert-buty-lcyclopentadienyl lithium
  • catalysts embodying the present invention are highly effective in the polymerization of propylene to produce isotactic polypropylene.
  • the isotactic polypropylene produced in accordance with the present invention will take the form of propylene homopolymer, although small amounts of co- monomers, such as ethylene, typically in amounts less than 5 weight % of the total feedstream, may be employed.
  • the cyclopentadienyl group is preferably substituted at the 3 position with a tertiary butyl group or a similarly relatively bulky group and at the 5 position with a substituent of lower molecular weight.
  • the cyclopentadienyl group may take the form of substituents with an isobutyl group at the 3 position and a methyl group at the 5 position.
  • the fluorenyl group preferably is di-substituted at the 2 and 7 positions as described previously and also substituted at the 4 position with a phenyl group or substituted phenyl group.
  • ligand structures characterized by 3-tertiary butyl cyclopentadienyl, 2,7-ditertiary butyl, 4-phenyl (or 4- tertiary butyl) fluorenyl group and the corresponding ligand structure which is also substituted on the cyclopentadienyl group at the 5 position with a methyl group.

Abstract

L'invention concerne des compositions de catalyseur et des procédés utilisés pour polymériser des monomères insaturés éthyléniquement, pour produire des polymères, spécifiques de la polymérisation du propylène, afin de produire du polypropylène isotactique et un copolymère, notamment un copolymère éthylène-propylène. Un catalyseur de polymérisation oléfinique est caractérisé par la formule: B(FluA)MQn dans laquelle Flu est un groupe fluorényle substitué en position 4 (ou 5) par un groupe hydrocarbyle volumineux ayant au moins 3 atomes de carbone; A est un groupe cyclopentadiényle ou indényle substitué ou non substitué ou un groupe hétéro-organo, XR, où X est un hétéroatome du groupe 15 ou 16 tel que l'azote, R est un groupe alkyle ou un groupe cycloalkyle ou un groupe aromatique mononucléaire qui peut être substitué ou non substitué; B est un pont de structure qui confère de la stéréo-rigidité à la structure du ligand. Le pont B est caractérisé par la formule ER'R', dans laquelle E est un atome de carbone, de silicium ou de germanium et R' et R' désignent chacun indépendamment un groupe alkyle, un groupe aromatique ou un groupe cycloalkyle; M est un métal de transition du groupe 4 ou du groupe 5 tel que titane, zirconium ou hafnium; Q est un atome de chlore, de brome, d'iode, un groupe alkyle, un groupe amino ou un groupe aromatique; n vaut 1 ou 2. Le groupe fluorényle peut être substitué à la fois en position 4 et en position 5 par un groupe hydrocarbyle volumineux contenant au moins 3 atomes de carbone. A peut prendre la forme d'un groupe indényle qui est substitué ou non substitué ou d'un groupe cyclopentadiényle qui est substitué en position 3 ou en position 3 et en position 5. Le groupe fluorényle peut être monosubstitué en position 4 (ou 5), sinon il est non substitué ou disubstitué aux positions 2,7 par des groupes alkyle, phényle ou phényle substitué.
PCT/US2005/000109 2005-01-04 2005-01-04 Composants de catalyseur et leur utilisation dans la polymerisation d'olefines WO2006137818A1 (fr)

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JP2015174859A (ja) * 2014-03-18 2015-10-05 三井化学株式会社 遷移金属化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法

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US5474962A (en) * 1992-09-22 1995-12-12 Mitsubishi Petrochemical Company Limited Powder catalyst composition and process for polymerizing olefins with the use thereof
US6063725A (en) * 1995-11-07 2000-05-16 Mitsui Chemicals, Inc. Olefin polymerization catalyst system
US6639030B2 (en) * 1994-10-25 2003-10-28 Tosoh Corporation Process for production of olefin polymer

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US5474962A (en) * 1992-09-22 1995-12-12 Mitsubishi Petrochemical Company Limited Powder catalyst composition and process for polymerizing olefins with the use thereof
US6639030B2 (en) * 1994-10-25 2003-10-28 Tosoh Corporation Process for production of olefin polymer
US6063725A (en) * 1995-11-07 2000-05-16 Mitsui Chemicals, Inc. Olefin polymerization catalyst system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015174859A (ja) * 2014-03-18 2015-10-05 三井化学株式会社 遷移金属化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法

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