WO1998006728A1 - Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine - Google Patents

Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine Download PDF

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WO1998006728A1
WO1998006728A1 PCT/US1997/013171 US9713171W WO9806728A1 WO 1998006728 A1 WO1998006728 A1 WO 1998006728A1 US 9713171 W US9713171 W US 9713171W WO 9806728 A1 WO9806728 A1 WO 9806728A1
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Prior art keywords
metal complex
hydrocarbyl
inden
dimethyl
group
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PCT/US1997/013171
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English (en)
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Jerzy Klosin
William J. Kruper, Jr.
Peter N. Nickias
Jasson T. Patton
David R. Wilson
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The Dow Chemical Company
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Priority to EP97937033A priority Critical patent/EP1021454A1/fr
Priority to SK152-99A priority patent/SK15299A3/sk
Priority to BR9711115A priority patent/BR9711115A/pt
Priority to AU39647/97A priority patent/AU716659B2/en
Priority to JP10509760A priority patent/JP2000516608A/ja
Priority to NZ333877A priority patent/NZ333877A/xx
Priority to CA002262377A priority patent/CA2262377A1/fr
Priority to HU9904148A priority patent/HUP9904148A3/hu
Publication of WO1998006728A1 publication Critical patent/WO1998006728A1/fr
Priority to NO990546A priority patent/NO990546L/no

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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
    • 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
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/6592—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

Definitions

  • This invention relates to a class of metal complexes, the ligands used to prepare these metal complexes and to olefin polymerization catalysts derived therefrom that are particularly suitable for use in a polymerization process for preparing polymers by polymerization ol ⁇ -olefins and mixtures of ⁇ -olefins
  • U S Patent No 's 5,350,817 and 5,304,614 disclose zirconium complexes with b ⁇ dged-metallocene ligands, wherein two indenyl groups are covalently linked together by a bridge containing carbon or silicon, which are useful for the polymerization of propylene
  • EP-A-577,581 discloses unsymmetrical bis-Cp metallocenes containing a fluorene ligand with heteroatom substituents E. Barsties; S. Schaible; M.-H. Prosenc; U. Rief; W. Roll, O. Weyland; B Dorerer; H.-H. B ⁇ ntzinger J Organometalhc Chem. 1996, 520, 63-68, and H. Plenio, D. birth J Organometalhc Chem.
  • Organometallics, 1992, 11, 21 15-2122 discloses Co-bridged bis-indenyl metallocenes with oxygen in the 5,6-pos ⁇ t ⁇ ons of the indenyl group, while N. Piccolravazzi, P Pino, G. Consigho; A Sironi, M. Moret Organometallics, 1990, 9, 3098-3105 discloses non-bridged bis-indenyl metallocenes with oxygen in the 4- and 7-pos ⁇ t ⁇ ons of the indenyl group.
  • M is a metal from one of Groups 3 to 13 of the Periodic Table of the
  • R independently each occurrence is hydrogen, or, is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl.
  • Z is a divalent moiety bound to both Cp and M via ⁇ -bonds, where Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen,
  • X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, ⁇ -bound ligand groups,
  • X' independently each occurrence is a neutral Lewis base ligating compound having up to 20 atoms
  • p is zero, 1 or 2, and is two less than the formal oxidation state of M, when X is an anionic ligand, when X is a dianionic ligand group, p is 1 , and
  • the above complexes may exist as isolated crystals optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, as well as in the form of a dimer or chelated derivative thereof, wherein the chelating agent is an organic material, preferably a neutral Lewis base, especially a t ⁇ hydrocarbylamine, t ⁇ hydrocarbylphosphine, or halogenated derivative thereof
  • a catalyst system for olefin polymerization prepared from catalyst system components comprising (A) a catalyst component comprising a metal complex of one of the aforementioned complexes, and
  • (B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1 10,000 to 100 1 , or activation of (A) by use of an activating technique
  • (B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from I 10,000 to 100 1
  • the metal complex is in the form of a radical cation
  • a preferred process of this invention is a high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more C2-20 ⁇ -olefins under polymerization conditions with one of the aforementioned catalyst systems at a temperature from about 100°C to about 250°C
  • This invention also provides a cyclopentadienyl-containing ligand of one of the aforementioned metal complexes where the ligand is in the form of
  • the present catalysts and processes result in the highly efficient production of high molecular weight olefin polymers over a wide range of polymerization conditions, and especially at elevated temperatures They are especially useful tor the solution or bulk polymerization of ethylene/propylene (EP polymers), ethylene/octene (EO polymers), cthylene/styrene (ES polymers), propylene and ethylene/propylene/diene (EPDM polymers) wherein the diene is ethylidenenorbomene, 1 ,4-hexad ⁇ ene or similar nonconjugated dienc
  • EP polymers ethylene/propylene
  • EO polymers ethylene/octene
  • ES polymers cthylene/styrene
  • EPDM polymers ethylene/propylene/diene
  • the diene is ethylidenenorbomene, 1 ,4-hexad ⁇ ene or similar nonconjugated dienc
  • the catalysts of this invention may also be supported on a support material and used in olefin polymerization processes in a slurry or in the gas phase
  • the catalyst may be prepolyme ⁇ zed with one or more olefin monomers in situ in a polymerization reactor or in a separate process with intermediate recovery of the prepolyme ⁇ zed catalyst prior to the primary polymerization process
  • Figure 1 shows the crystal structure of d ⁇ chloro(N-( l , l-d ⁇ methylethyl)-l, l- dimethyl- 1 -(( 1.2.3,3a,7a- ⁇ )-2-d ⁇ methylam ⁇ no- 1 H-inden- 1 -y l)s ⁇ lanam ⁇ nato-(2-)-N-)- titanium.
  • Figure 2 shows the crystal structure of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1- (( 1 ,2,3.3a,7a- ⁇ )-2-ethoxy- 1 H-inden- 1 -yl)s ⁇ lanam ⁇ nato-(2-)-N-)-d ⁇ methyl-t ⁇ tan ⁇ um.
  • Olefins as used herein are C2-20 aliphatic or aromatic compounds containing vinylic unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, and norbornene, including norbornene substituted in the 5- and 6- positions with C l-20 hydrocarbyl groups Also included are mixtures of such olefins as well as mixtures of such olefins with C4.40 diolefin compounds Examples of the latter compounds include ethy dene norbornene, 1 ,4-hexad ⁇ ene, norbornadiene, and the like.
  • the catalysts and processes herein are especially suited for use in preparation of ethylene/1 -butene, ethylene/1 -hexene, ethylene/styrene, ethylene/propylene, ethylene/1 -pentene, ethylene/4-methyl-l-pentene and ethylene/1-octene copolymers as well as terpolymers of ethylene, propylene and a nonconjugated diene, such as, for example, EPDM terpolymers
  • Preferred X' groups are carbon monoxide, phosphines, especially t ⁇ methylphosphine, t ⁇ ethylphosphine, t ⁇ phenylphosphine and b ⁇ s(l ,2- d ⁇ methylphosph ⁇ no)ethane, P(OR')3, wherein R 1 is hydrocarbyl, silyl or a combination thereof, ethers, especially tetrahydrofuran, amines, especially py ⁇ dine, bipy ⁇ dine, tetramethylethylenediamine (TMEDA), and triethylamine, olefins, and conjugated dienes having from 4 to 40 carbon atoms Complexes including the latter X' groups include those wherein the metal is in the +2 formal oxidation state
  • Preferred coordination complexes according to the present invention are complexes corresponding to the formula
  • R ⁇ , R ⁇ R * and R ⁇ are R groups, each of which independently is hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each of R ⁇ , R ⁇ , R ⁇ and R ⁇ optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, d ⁇ (hydrocarbyls ⁇ lyl)am ⁇ no, hydrocarbylamino, d ⁇ (hydrocarbyl)am ⁇ no, d ⁇ (hydrocarbyl)phosph ⁇ no, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl,
  • R ⁇ , R ⁇ , R A and R B are covalently linked with each other to form one or more fused rings or ring systems having from 1 to 80 nonhydrogen atoms for each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino.
  • R ⁇ groups are those wherein R A IS hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl and T is O or N, more preferred are those wherein R A u, hydrocarbyl or hydrocarbylsilyl and T is O or N, and still more preferred are wherein RA IS hydrocarbyl or hydrocarbylsilyl and T is O
  • Preferred heteroatom-containing substituents at the 2-pos ⁇ t ⁇ on of the Cp are those wherein the (R A ),-T group dimethylamino, diethylamino, methylethylamino, methylphenylammo, dipropylamino, dibutylammo, pipe ⁇ dinyl, morpholinyl, pyrro dinyl, hexahydro-l H-azepin- l-yl, hexahydro-l(2H)-azoc ⁇ nyl, octahydro- 1 H- azon ⁇ n- 1-yl, octahydro- l(2H)-azec ⁇ nyl, methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1-d ⁇ methyethyloxy, t ⁇ methylsiloxy or l , l-d ⁇ methylethyl(d ⁇ methyls ⁇ lyl)oxy
  • (RA).-T group is methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1-d ⁇ methyethyloxy, t ⁇ methylsiloxy, 1 , 1 - d ⁇ methylethyl(d ⁇ methyls ⁇ lyl)oxy
  • either the ligand or metal complex has one or more fused rings or ring systems in addition to the Cp or indenyl wherein the one or more fused rings or ring systems contain one or more ring heteroatoms which are N, O. S, or P Preferred ring heteroatoms are N or O, with N being more highly preferred.
  • metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
  • Y is -O-, -S-, -NR*-, -PR*-,
  • R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system,
  • X is independently each occurrence methyl, benzyl, t ⁇ methylsilylmethyl, allyl, pyrollyl or two X groups together are 1 ,4-butane-d ⁇ yl, 2-butene- 1 ,4-d ⁇ yl, 2,3-d ⁇ methyl-2-butene- 1 ,4-d ⁇ yl, 2-methyl-2-butene-l ,4-d ⁇ yl, or xylyldiyl
  • metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
  • Y is -O-, -S-, -NR*-, -PR*-,
  • R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R x group from Y form a ring system,
  • metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M.
  • Y is -O-, -S-, -NR*-, -PR*-
  • R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system;
  • metals can be used in the preparation of the metal complexes of this invention, desirably a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, which is in the +2, +3 or +4 formal oxidation state, more desirably a metal from one of Groups 3 to 13
  • Metal complexes of this invention having somewhat different characteristics are those where M is a metal from one of Groups 3-6, one of Groups 7-9 or one of Groups 10-12. Preferred are those where M is a metal from Group 4, desirably Ti, Zr or Hf, with Ti and Zr being more preferred.
  • Ti is the most highly preferred metal, especially for use in complexes which contain only one Cp-contaming ligand which is the heteratom- containing ligand of this invention, while Zr is highly preferred for use in complexes which contain two Cp-containmg ligands, at least one of which is a heteratom- containing ligand.
  • Ti is in the +4 formal oxidation state, while, alternatively it is preferred that Ti is in the +3 formal oxidation state, and more preferred is that Ti is in the +2 formal oxidation state
  • Zr is in the +4 formal oxidation state, or, alternatively, in the +2 formal oxidation state
  • Y is -NR ⁇ with the more preferred -NR* being those where R* is a group having a primary or secondary carbon atom bonded to N Highly preferred are those where R* is cyclohexyl oi isopropyl
  • the complexes can be prepared by use of well known synthetic techniques
  • a reducing agent can be employed to produce the lower oxidation state complexes
  • a suitable noninterfe ⁇ ng solvent at a temperature from -100 to 300°C, preferably from -78 to 100°C, most preferably from 0 to 50°C
  • reducing agent herein is meant a metal or compound which, under reducing conditions causes the metal M, to be reduced from a higher to a lowei oxidation state
  • suitable metal reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy
  • suitable reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium
  • Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C [_4 dialkyl ethers, C j _4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoing are also suitable
  • R, R' , R", R" ⁇ R"" independently selected in each case are H (except on the nitrogen bound directly to the cyclopentadienyl ring), alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, and are not limited only to these groups
  • the heteroatom-containing substituent has a nitrogen in the 2-pos ⁇ t ⁇ on of the indenyl system.
  • 2-Indanone is a convenient starting material for conversion to the corresponding enamine, although formation of the latter is not restricted to the use of this compound.
  • Enamines of indanone are typically formed by methods known in the art, including condensation of secondary amines with the ketone in anhydrous alcohol (U. Edlund Acta Chemica Scandinavica, 1974, 27, 4027-4029).
  • enamines of 2- ⁇ ndanone are more easily formed by amine condensation than 1 -indanone analogues.
  • ste ⁇ cally hindered ketones such as l -methyl-2- ⁇ ndanone or more volatile amines such as dimethyl amine
  • dehydrating reagents such as titanium chloroamides (generated in situ from titanium tetrachlo ⁇ de and the condensation amine) (R. Carlson, A Nilsson Acta Chemica Scandinavica B 38, 1984, 49-53).
  • titanium chloroamides generated in situ from titanium tetrachlo ⁇ de and the condensation amine
  • R. Carlson A Nilsson Acta Chemica Scandinavica B 38, 1984, 49-53
  • These two methods have been employed to produce enamines substituted in the 2-pos ⁇ t ⁇ on of the indene (the 1 -position is typically bonded to a silicon or other linking moiety in subsequent compounds).
  • Another method for the preparation of enamines involves electrophilic amination of carbanions such as lithium indenide (E. Erdik, M, Ay Chem Rev.. 1989
  • enamines prepared by these routes must be highly pure and free of ketone, Aldol by-products and higher weight reaction tars which typically accompany product formation. None of the aforementioned routes uniformly provides a product which can be used without some sort of further purification
  • chromatographic purification using flash-grade silica gel or alumina rapidly promotes hydrolysis of the enamine to free amine and ketone, an unfortunate consequence.
  • enamines of this nature may be purified by careful fractional distillation, or occasionally, recrystallization. In particular, rapid distillation of indanone enamines is required to prevent thermal polymerization in the still at elevated temperature.
  • R, R', R", R'", R" independently selected in each case are H (except on oxygen), alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, and are not limited only to these groups.
  • enol ethers in this position can be made by dehydration of the appropriate hemiketal which is formed in situ from indanone and alcohol in theistnce of an acidic catalyst (L A Paquette, A Varadarajan, E Bey J Am Chem Soc 1984, 106, 6702-6708, W E Parham, C D Wright J Org Chem 1957, 22, 1473-77)
  • Silyl enol ethers can be made by forming the enolate of 2- ⁇ ndanone and quenching with, for example, t-butyl-dimethylsilyl chloride (R Leino, H Luttikhedde C E Wilen, R Sillanpa, J H Nasman, Organometallics, 1996, 15, 2450-2453)
  • Enol ethers of indanones like the enamine analogues, are also susceptible to hydrolysis and are very oxygen sensitive Once purified, they are best expediently converted to their corresponding
  • conversion of the enamine to its corresponding anionic salt may be accomplished by reaction with an appropriate base of suitable strength in an appropriate noninteife ⁇ ng solvent Under appropriate, anaerobic, anhydrous conditions, the often solid anionic salt may be filtered, washed and dried in nearly quantitative yield Likewise, enol ethers of 2- ⁇ ndanone can be deprotonated to the corresponding anionic salt
  • suitable base is more restricted in the case of silyl enol ethers, since certain bases, like n-butyllithium, were found to cause desilylation with generation of the enolate anion (base attack on the silyl group)
  • CGC-ligand constrained geometry ligands
  • a cyclopentadienyl anion is reacted with electrophiles such as halogenated secondary alkylamines or halogenated secondary silylamines to give the corresponding cyclopentadienyl alkylamine or cyclopentadienyl silylamme
  • electrophiles such as halogenated secondary alkylamines or halogenated secondary silylamines
  • solvents suitable for the preparation of the anionic salts and dianionic salts of the invention include, but are not limited to aliphatic and aromatic hydrocarbons, particularly straight and branched chain hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, including their branched isomers and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyciohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene and mixtures thereof; ethers and cyclic ethers
  • Bases of suitable strength for the preparation of the dianionic salts of the invention include hydrocarbyl salts of Group 1 and Group 2 metals, especially alkyl or aryl salts of lithium or magnesium, such as methyllithium, ethyllithium, n- butyllithium, s-butyllithium, t-butyllithium, phenyllithium, methyl magnesium chloride, ethyl magnesium bromide, i-propyl magnesium chloride, dibutylmagnesium, (butyl)(ethyl)magnesium, dihexylmagnesium; Group 1 or Group 2 metals, such as lithium, sodium, potassium and magnesium; Group 1, Group 2 or Group 13 metal hydrides, such as lithium hydride, sodium hydride, potassium hydride or lithium aluminum hydride.
  • Group 1 or Group 2 metal amide complexes such as lithium diisopropylamidc, lithium dimethylamide, lithium hexamethyldisilazide, so
  • Bases of suitable strength for the preparation of the anionic salts of the invention include the foregoing as well as Group 1 or Group 2 metal alkoxide complexes, such as sodium ethoxide, sodium t- butoxide, potassium butoxide and potassium amylate
  • the metallation of the dianionic salt may be accomplished by methods cited in this art as well. Reaction of the dianionic salt in THF with TiCl 3 (THF followed by oxidation with methylene chloride or lead dichlo ⁇ de is a well established procedure (J. Okuda, S. Verch, T. P. Spaniol, R. Stur er Chem. Ber., 1996, 129, 1429- 1431, D. D Devore EP 514,828) which affords the titanium (IV) dichlo ⁇ de complex.
  • the dichlo ⁇ de may be silylated or hydrocarbylated by ligand exchange with an appropriate silylating or hydrocarbylating agent, such as methyllithium, methyl magnesium chloride, benzyl potassium, allyl lithium, t ⁇ methyisilylmethyl lithium, neopentyl magnesium bromide and phenylhthium.
  • an appropriate silylating or hydrocarbylating agent such as methyllithium, methyl magnesium chloride, benzyl potassium, allyl lithium, t ⁇ methyisilylmethyl lithium, neopentyl magnesium bromide and phenylhthium.
  • the formation of the CGC metal (III) complexes according to the invention can be accomplished by any of several synthesis methods, among which are the following:
  • the reaction under anaerobic and anhydrous conditions of the dianionic salts with t ⁇ valent metal salts, such as Group 4 metal (III) halide or alkoxide complexes can be carried out, optionally followed by silylation or hydrocarbylation with suitable silylating or hydrocarbylating agents, to form the corresponding CGC metal (III) halide, alkoxide, silyl or hydrocarbyl complexes of the invention
  • a further synthesis method involves reducing an appropriate CGC metal (IV) dihahde or dialkoxide complex, or, preceded by monosilylation or monohydrocarbylation, the corresponding CGC (IV) silyl or hydrocarbyl monohalide or monoalkoxide complex with a suitable reducing agent to the corresponding CGC metal (III) halide, alkoxide, silyl or hydrocarbyl complex
  • CGC metal (III) complexes are the methods described by Wilson (D R Wilson US 5,504,224, 1996) which is incorporated herein by reference
  • cyclopentadienyl ligands can be displaced by the dianionic salts and/or by the (stabilizing) hydrocarbylating agents from cyclopentadienyl-containing Group 4 metal complexes m the +3 oxidation state to give the CGC metal (III) complexes of the invention
  • Suitable reducing agents for reducing the oxidation state of the metals of the CGC metal (IV) complexes from +4 to +3 have been described above and especially include zinc, aluminum and magnesium
  • Suitable silylating and hydrocarbylating agents for the CGC metal (III) complexes and the CGC metal (IV) complexes of the invention include alkyl, such as methyl, ethyl, propyl, butyl, neopentyl and hexyl, aryl, such as phenyl, naphthyl and biphenyl, aralkyl, such as benzyl, tolylmethyl, diphenylmethyl; alkaryl, such as tolyl and xylyl, allyl, silyl- or alkyl-substituted allyl, such as methylallyl, t ⁇ methylsilylallyl, dimethylallyl and t ⁇ methylallyl, t ⁇ alkylsilyl, such as t ⁇ methylsilyl and t ⁇ ethylsilyl, t ⁇ alkylsilylalkyl, such as t ⁇ methylsilylmethyl, pentadienyl, alky
  • dialkylaminoalkaryl such as o-(N,N- dimethylaminomethyOphenyl
  • dialkylammoaralkyl such as o-(N,N- dimethylamino)benzyl
  • salts of Group 1 , 2 or 13 metals preferably the salts of lithium, sodium, potassium, magnesium and aluminum.
  • Preferred silylating and hydrocarbylating agents include trimethylaluminum, methyllithium, methyl magnesium chloride, neopentyllithium, trimethylsilylmethyi magnesium chloride and phenyllithium.
  • Stabilizing group-containing hydrocarbylating agents are also included, especially the stabilizing group-containing hydrocarbylating agents and salts of the stabilizing group-containing hydrocarbyl groups described in US 5,504,224, whose salts include, for example, benzyl potassium, 2-(N,N-dimethylamino)benzyllithium, allyllithium and dimethylpentadienyl potassium.
  • the stabilizing groups are further described in U.S. Ser. No. 8003, filed Jan. 21 , 1993 (corresponding to WO 93/19104), incorporated herein by reference.
  • Preferred halides or alkoxides of the metal (III) halide or alkoxide complexes and the CGC metal (III) halide or alkoxide complexes include fluoride, chloride, bromide, iodide, methoxide, ethoxide, i-propoxide, n- propoxide, butoxide and phenoxide.
  • Preferred metal (III) halide or alkoxide complexes include titanium (III) chloride, titanium (III) ethoxide, titanium (III) bromide, titanium (III) isopropoxide, titanium (III) (dichloro)(isopropoxide), as well as Lewis base complexes of the foregoing, especially ether complexes thereof, particularly diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether complexes thereof.
  • Preferred cyclopentadienyl-containing Group 4 metal complexes in the +3 oxidation state include triscyclopentadienyl titanium, biscyclopentadienyl titanium chloride, biscyclopentadienyl titanium bromide, biscyclopentadienyl titanium isopropoxide, cyclopentadienyl titanium dichloride, cyclopentadienyl titanium diphenoxide, cyclopentadienyl titanium dimethoxide and bis((trimethylsilyl)(t- butyl )cyclopentadienyl)zirconium chloride.
  • the ligands of this invention are 2-heteroatom substituted cyclopentadienyl- containing ligands where the ligand is in the form of:
  • a ligand of this invention for synthesis to produce a metal complex of this invention, or for synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the ianthanides or actinides, and from 1 to 4 of the ligands.
  • the ligands of this invention may be used in various forms, including salts, with various groups attached at the Z position in syntheses leading to metal complexes in which the metal is from Groups 3-16 of periodic table or the Ianthanides, and in which from one to four of these ligands, alone or in combination with other ligands, are present in the metal complex.
  • the methods of synthesis may be similar or analogous to those discussed herein for the Group 4 metal complexes of this invention, as well as various other synthetic procedures known in the art.
  • the metal complexes are useful as catalysts in various reactions, including olefin polymerization reactions.
  • x is 0 or 1
  • y is 0 or 1
  • z is 0 or 1
  • x + y is 0 or 1
  • x + z is 0 or 1
  • the other symbols are as previously defined, where the dotted circle within the Cp ring implies the various possibilities for double bond character, partial double bond character or aromatic character as appropriate, depending upon the values for x, y, and z
  • the complexes are rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique.
  • Suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, t ⁇ isobutyl aluminum modified methylalumoxane, or lsobutytalumoxane; neutral Lewis acids, such as C 1.45 hydrocarbyl substituted Group
  • Combinations of neutral Lewis acids especially the combination of a t ⁇ alkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated t ⁇ (hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially t ⁇ s(pentafluorophenyl)borane, t ⁇ s(o- nonafluorobiphenyOborane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially t ⁇ s(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane are especially desirable activating cocatalysts
  • a benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of t ⁇ s(pentafluorophenyl)borane/alumoxane mixture occurs at reduced levels of alumoxan
  • Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion,
  • noncoordinating means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base
  • a noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes
  • “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfe ⁇ ng with desired subsequent polymerization or other uses of the complex
  • Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nit ⁇ les.
  • Suitable metals include, but are not limited to, aluminum, gold and platinum.
  • Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom arc, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially
  • cocatalysts may be represented by the following general formula
  • L* is a neutral Lewis base
  • (L*-H)+ is a Bronsted acid
  • ( )d- is a noncoordinating, compatible anion having a charge of d-
  • d is an integer from 1 to 3
  • (A)d- corresponds to the formula. [MO4] ,
  • M' is boron or aluminum in the +3 formal oxidation state
  • Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.
  • suitable hydrocarbyloxide Q groups are disclosed in U.S. Patent 5,296,433, the teachings of which are herein incorporated by reference.
  • d is one, that is, the counter ion has a single negative charge and is A " .
  • Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
  • B is boron in a formal oxidation state of 3
  • Q is a hydrocarbyl-, hydrocarbyloxy-, fluo ⁇ nated hydrocarbyl-, fluo ⁇ nated hydrocarbyloxy-, or fluo ⁇ nated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
  • Q is each occurrence a fluo ⁇ nated aryl group, especially, a pentafluorophenyl group.
  • Illustrative, but not limiting, examples of ion forming compounds comprising proton donatable cations which may be used as activating cocatalysts in the preparation of the catalysts of this invention are t ⁇ -substituted ammonium salts such as: t ⁇ methylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, t ⁇ ethylammonium tetraphenylborate, t ⁇ propylammonium tetraphenylborate, t ⁇ (n-butyl)ammon ⁇ um tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate,
  • Dialkyl ammonium salts such as d ⁇ -( ⁇ -propy ] )ammon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate, and dicyclohexylammonium tetrak ⁇ s(pentafluorophenyl)borate
  • T ⁇ -substituted phosphonium salts such as triphenylphosphonium tetrak ⁇ s(pentafluorophenyl)borate, t ⁇ (o-tolyl)phosphon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate, and t ⁇ (2 6-d ⁇ methylphenyl)phosphon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate
  • An especially preferred group of activating cocatalysts is t ⁇ s(pentafluorophenyl)borane, N-R3.N-R4 anilinium tetrak ⁇ s(pentafluorophenyI)borate where R3 and R4 independently each occurrence are substituted or unsubstituted saturated hydrocarbyl groups having from 1 to 8 carbon atoms, (R ⁇ R2NHCH3) + (C 6 H 4 OH)B(C 6 F 5 ) 3 , or (R 1 R 2 NHCH 3 ) + B(C 6 F 5 ) 4 , where R ⁇ and R 2 independently each occurrence are substituted or unsubstituted saturated hydrocarbyl groups having from 12 to 30 carbon atoms
  • Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula
  • Ox e+ is a cationic oxidizing agent having a charge of e+, e is an integer from 1 to 3, and A 0" - and d are as previously defined
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl- substituted ferrocenium, Ag + ' or Pb + 2
  • Preferred embodiments of A ⁇ " are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrak ⁇ s(pentafluorophenyl)borate.
  • Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula.
  • ⁇ + is a C ] _20 carbenium ion
  • a " is as previously defined
  • a preferred carbenium ion is the t ⁇ tyl cation, i.e triphenyl methy hum
  • a further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula
  • R is C ] _ ⁇ o hydrocarbyl, and X', q and A " aie as previously defined.
  • Preferred silylium salt activating cocatalysts are t ⁇ methylsilylium tetrakispentafluorophenylborate, t ⁇ ethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof.
  • Silylium salts have been previously gene ⁇ cally disclosed in J Chem Soc Chem Comm., 1993, 383-384, as well as Lambert, J B , et al , Organometallics, 1994, 13, 2430-2443
  • the use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in United States Patent Application entitled, "Silylium Cationic Polymerization Activators For Metallocene Complexes", filed in the names of David Neithamer, David Devore, Robert LaPointe and Robert Mussell on September 12, 1994
  • the technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion.
  • solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction
  • suitable solvents are materials that are liquids under the conditions of the electrolysis (generally temperatures from 0 to 100°C), capable of dissolving the supporting electrolyte, and inert "Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis
  • Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME), and mixtures thereof
  • the electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively) Suitable materials of construction for the cell are glass, plastic, ceramic and glass coated metal
  • the electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions Platinum or palladium are preferred inert conductive materials Normally an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment
  • the working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex
  • the counter electrode is immersed in a mixture of the solvent and supporting electrolyte
  • the desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte
  • Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion,
  • A- Preferred supporting electrolytes are salts corresponding to the formula G + A ; wherein.
  • G + is a cation which is nonreactive towards the starting and resulting complex
  • A" is as previously defined.
  • Examples of cations, G + include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms.
  • Preferred cations are the tetra(n-butylammon ⁇ um)- and tetraethylammonium- cations
  • the cation of the supporting electrolyte passes to the counter electrode and A" migrates to the working electrode to become the anion of the resulting oxidized product.
  • Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode.
  • Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrak ⁇ s(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, especially tetra(n- butylammon ⁇ um)tetrakis(pentafluorophenyl) borate.
  • a further recently discovered electrochemical technique for generation of activating cocatalysts is the electrolysis of a disilane compound in the presence of a source of a noncoordinating compatible anion.
  • This technique is more fully disclosed and claimed in the previously mentioned United States Patent application entitled, "Silylium Cationic Polymerization Activators For Metallocene Complexes", filed on September 12, 1994.
  • the foregoing electrochemical activating technique and activating cocatalysts may also be used in combination
  • An especially preferred combination is a mixture of a t ⁇ (hydrocarbyl)alum ⁇ num or t ⁇ (hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound
  • the molar ratio of catalyst/cocatalyst employed preferably ranges from 1 10,000 to 100 1 , more preferably from 1 -5000 to 10 1 , most preferably from 1 1000 to 1 1
  • Alumoxane, when used by itself as an activating cocatalyst, is employed in large quantity, generally at least 100 times the quantity of metal complex on a molar basis T ⁇ s(pentafluorophenyl)borane, where used as an activating cocatalyst, is employed in a molar ratio to the metal complex of form 0 5 1 to 10 1 , more preferably from 1 I to 6' 1 , most preferably from 1 1 to 5 1
  • the remaining activating cocatalysts are generally employed in approximately equimolar quantity with the metal complex
  • the process may be used to polymerize ethylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination
  • Preferred monomers include monoviny dene aromatic monomers, especially styrene, 4-v ⁇ nylcyclohexene, vinylcyclohexane, norbornadiene and C2- ] ⁇ aliphatic ⁇ -olefins, especially ethylene, propylene, isobutylene, 1 -butene, 1 -pentene, 1 -hexene, 3-methyl- l-pentene, 4-methyl- 1-pentene, 1 -heptene, and 1-octene, C4.40 dienes, and mixtures thereof
  • Most preferred monomers are ethylene, propylene, 1 -butene, 1 -hexene, 1 -octene nd mixtures of ethylene, propylene and a nonconjugated diene, especially ethylidenenorbo
  • the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250°C, preferably 30 to 200°C and pressures from atmospheric to 10,000 atmospheres Suspension, solution, slurry, gas phase, bulk, solid state powder polymerization or other process condition may be employed if desired
  • a support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase or slurry polymerization process.
  • the support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1 : 100,000 to 1.10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 - 10,000 to 1 :30.
  • One such polymerization process comprises contacting, optionally in a solvent, one or more ⁇ -olefins with a catalyst according to the present invention, in one or more continuous stirred tank or tubular reactors, connected in series or parallel, or in the absence of solvent, optionally in a fluidized bed gas phase reactor, and recovering the resulting polymer. Condensed monomer or solvent may be added to the gas phase reactor as is well known in the art.
  • the molar ratio of catalyst:polyme ⁇ zable compounds employed is from 10 ⁇ ' -: 1 to 10 " ' : 1 , more preferably from l ⁇ X l to 10" 5 : 1.
  • Suitable solvents for polymerization are inert liquids.
  • examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyciohexane.
  • cycloheptane methylcyclohexane, mcthylcycloheptane, and mixtures thereof; perfluo ⁇ nated hydrocarbons such as perfluo ⁇ nated C4_ J O alkanes, and the like and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like.
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, 1 - butene, cyclopentene, 1 -hexene, 1 -heptene, 4-v ⁇ nylcyclohexene, vinylcyclohexane, 3- methyl- 1 -pentene, 4-methyl-l-pentene, 1 ,4-hexad ⁇ ene, 1 -octene, 1 -decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), and the like. Mixtures of the foregoing are also suitable.
  • the catalyst systems may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.
  • An example of such a process is disclosed in WO 94/00500, equivalent to U S Serial Number 07/904,770, as well as U.S Serial Number 08/10958. filed January 29. 1993. the teachings oi which are hereby incorporated by reference herein
  • melt flow rates from 0 001 to 10 0 dg/ in are readily attained in a high temperature process
  • the catalyst systems of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/ ⁇ -olefin copolymers having high levels of long chain branching
  • the use of the catalyst systems of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch
  • the use of the present catalysts system advantageously allows for the economical production of ethylene/ ⁇ -olefin copolymers having processabi ty similar to high pressure, free radical produced low density polyethylene
  • a preferred process is a high temperature solution polymerization process for the polymerization of oletins comprising contacting one or more C2-20 ot-olefins under polymerization conditions with a catalyst system of this invention at a temperature from about 100°C to about 250°C More preferred as a temperature range for this process is a temperature from about 120°C to about 200°
  • the present catalyst systems may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/ ⁇ -olefin mixtures with low levels of a "H" branch inducing diene, such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • a "H" branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • a "H” branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • a "H” branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • such polymers are produced in a solution piocess. most preferably a continuous solution process Alternatively such polymers may be produced in a gas phase process or a slurry process
  • the present catalyst system is particularly useful in the preparation of EP and EPDM copolymers in high yield and productivity
  • the process employed may be either a solution or slurry process both of which are previously known in the art Kaminsky. J Poly Sci . Vol 23, pp 2151 -64 ( 1985) repo ⁇ ed the use of a soluble b ⁇ s(cyclopentad ⁇ enyl) zirconium dimethyl-alumoxane catalyst system for solution polymerization of EP and EPDM elastomers
  • U S 5,229,478 disclosed a slurry polymerization process utilizing similar b ⁇ s(cyclopentad ⁇ enyl) zirconium based catalyst systems
  • an olefin polymerization catalyst to a diene, especially the high concentrations of diene monomer required to produce the requisite level of diene incorporation in the final EPDM product, often reduces the rate or activity at which the catalyst will cause polymerization of ethylene and propylene monomers to proceed
  • lower throughputs and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other ⁇ - olefin copolymer elastomer
  • the present catalyst system advantageously allows for increased diene reactivity thereby preparing EPDM polymers in high yield and productivity Additionally, the catalyst system of the present invention achieves the economical production of EPDM polymers with diene contents of up to 20 weight percent or higher, which polymers possess highly desirable fast cure rates
  • the nonconjugated diene monomer can be a straight chain, branched chain or cyclic hydrocarbon diene having from about 6 to about 15 carbon atoms.
  • suitable nonconjugated dienes are straight chain acyclic dienes such as 1 ,4-hexad ⁇ ene and 1 ,6-octad ⁇ ene, branched chain acyclic dienes such as 5-methyl-l ,4-hexad ⁇ ene, 3,7-d ⁇ methyl- l ,6-octad ⁇ ene, 3,7-d ⁇ methyl- l ,7-octad ⁇ ene and mixed isomers ol dihydromy ⁇ cene and dihydrooc ene, single ring alicyclic dienes such as 1 ,3-cyclopentad ⁇ ene, 1 ,4-cyclohexad ⁇ ene, 1 ,5-cyclooctad ⁇ ene and 1 ,5-cyclodode
  • 5-d ⁇ ene, alkenyl, alkylidene, cycloalkenyl and cycloalky dene norbornenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5- ⁇ sopropyl ⁇ dene-2- norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cycIohexyhdene-2-norbornene, 5- v ⁇ nyl-2-norbornene and norbornadiene
  • the particularly preferred dienes aie 1 ,4-hexad ⁇ ene (HD), 5-ethyl ⁇ dene-2-norbornene (ENB), 5-v ⁇ nyl ⁇ dene-2- noibornene (VNB), 5-methylene-2-norbornene (MNB ). and dicyclopentadiene (DCPD)
  • the especially preferred dienes are 5-ethyhdene-2-norbornene (ENB) and 1 ,4-hexad ⁇ ene (HD)
  • the preferred EPDM elastomers may contain about 20 up to about 90 weight percent ethylene, more preferably about 30 to 85 weight percent ethylene, most preferably about 35 to about 80 weight percent ethylene
  • alpha-olefins suitable for use in the preparation of elastomers with ethylene and dienes are preferably C3.
  • alpha-olefins Illustrative non-limiting examples of such alpha-olefins are propylene, 1 -butene 1 -pentene, 1 -hexene, 4- methyl- 1 -pentene, 1 -heptene, 1-octene, 1 -decene, and 1 -dodecene
  • the alpha-olefin is generally incorporated into the EPDM polymer at about 10 to about 80 weight percent, more preferably at about 20 to about 65 weight percent
  • the nonconjugated dienes are generally incorporated into the EPDM at about 0 5 to about 20 weight percent, more, preferably at about 1 to about 15 weight percent, and most preferably at 3 to about 12 weight percent If desired, more than one diene may be incorporated simultaneously, for example HD and ENB, with total diene incorporation within the limits specified
  • the catalyst system of this invention may comprise an aluminum organometalhc component which comprises an alumoxane, an aluminum alkyl or a combination thereof
  • This component may be present in a nonactivating amount and function primarily as a scavenger, or it may interact with the cocatalyst component to enhance the activity of the catalyst component, or it may do both
  • the catalyst or cocatalyst of the catalyst system can be covalently or lonically attached to the support material of the support component, which comprises a support material which is a polymer, an inorganic oxide, a metal halide, or a mixture thereof
  • Preferred supports for use in the present invention include highly porous silicas aluminas, aluminosilicates, and mixtures thereof
  • the most preferred support material is silica
  • the support material may be in granular, agglomerated, pelletized, or any other physical form. Suitable materials include, but are not limited to, silicas available from Grace Davison (division of W.R. Grace & Co ) under the designations SD 3216 30, Davison Syloid 245, Davison 948 and Davison 952, and from Crossfield under the designation ES70, and from Degussa AG under the designation Aerosil 812, and aluminas available from Akzo Chemicals Inc. under the designation Ketzen Grade B
  • Supports suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B E T. method from 10 to about 1000 n g, and preferably from about 100 to 600 ⁇ g.
  • the pore volume of the support, as determined by nitrogen adsorption, advantageously is between 0 1 and 3 cm ⁇ /g, preferably from about 0 2 to 2 c ⁇ X/g
  • the average particle size depends upon the process employed, but typically is from 0 5 to 500 ⁇ m, preferably from 1 to 100 ⁇ m.
  • Both silica and alumina are known to inherently possess small quantities of hydroxyl functionality.
  • these materials are preferably subjected to a heat treatment and/or chemical treatment to reduce the hydroxyl content thereof
  • Typical heat treatments are carried out at a temperature from 30°C to 1000°C (preferably 250°C to 800°C for 5 hours or greater) for a duration of 10 minutes to 50 hours in an inert atmosphere or under reduced pressure.
  • Typical chemical treatments include contacting with Lewis acid alkylating agents such as t ⁇ hydrocarbyl aluminum compounds, t ⁇ hydrocarbylchlorosilane compounds, t ⁇ hydrocarbylalkoxysilane compounds or similar agents. Residual hydroxyl groups are then removed via chemical treatment
  • Suitable functionalizing agents are compounds that react with surface hydroxyl groups of the support or react with the silicon or aluminum of the matrix. Examples of suitable functionalizing agents include phenylsilane, hexamethyldisilazane diphenylsilane, methylphenylsilane. dimethylsilane, diethylsilane, dichlorosilane, and dichlorodimethylsilane. Techniques for forming such functionahzed silica or alumina compounds were previously disclosed in U S Patents 3,687,920 and 3.879,368, the teachings of which arc herein incorporated by reference
  • the support may also be treated with an aluminum component selected from an alumoxane or an aluminum compound of the formula AIR ' x R- y , wherein R ' independently each occurrence is hydride or R, R- is hydride, R or OR, x' is 2 or 3, y' is 0 or 1 and the sum of x' and y' is 3
  • suitable R ' and R ⁇ groups include methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy
  • the aluminum component is selected from the group consisting of aluminoxanes and t ⁇ (C i .4 hydrocarbyOaluminum compounds Most preferred aluminum components are aluminoxanes. t ⁇ methylaluminum, t ⁇ ethylaluminum, t ⁇
  • Alumoxanes are oligomeric or polymeric aluminum oxy compounds containing chains of alternating aluminum and oxygen atoms, whereby the aluminum carries a substituent, preferably an alkyl group
  • the structure of alumoxane is believed to be represented by the following general formulae (-Al(R)-O) m ' , for a cyclic alumoxane, and R2Al-O(-Al(R)-O) rn '-AlR2, for a linear compound, wherein R is as previously defined, and m' is an integer ranging from I to about 50, preferably at least about 4
  • 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.
  • alumoxanes are methylalumoxane and methylalumoxane modified with minor amounts of C2-4 alkyl groups, especially isobutyl Alumoxanes generally contain minor to substantial amounts of starting aluminum alkyl compound
  • the treatment of the support material in order to also include optional alumoxane or t ⁇ alkylaluminum loadings involves contacting the same before, after or simultaneously with addition of the complex or activated catalyst hereunder with the alumoxane or trialkyialummum compound, especially t ⁇ ethylaluminum or tmsobutylaluminum.
  • the mixture can also be heated under an men atmosphere for a period and at a temperature sufficient to fix the alumoxane, trialkyialummum compound, complex or catalyst system to the support.
  • the treated support component containing alumoxane or the trialkyialummum compound may be subjected to one or more wash steps to remove alumoxane or trialkyialummum not fixed to the support.
  • the alumoxane may be generated in situ by contacting an unhydrolyzed silica or alumina or a moistened silica or alumina with a t ⁇ alkyl aluminum compound optionally in the presence of an inert diluent.
  • an unhydrolyzed silica or alumina or a moistened silica or alumina with a t ⁇ alkyl aluminum compound optionally in the presence of an inert diluent.
  • Suitable aliphatic hydrocarbon diluents include pentane, isopentane, hexane, heptane, octane, isooctane, nonane. isononane, decane, cyciohexane, methylcyclohexane and combinations of two or more of such diluents
  • Suitable aromatic hydrocarbon diluents are benzene, toluene, xylene, and other alkyl or halogen substituted aromatic compounds.
  • the diluent is an aromatic hydrocarbon, especially toluene
  • the residual hydroxyl content thereof is desirably reduced to a level less than 1 0 meq of OH per gram of support by any of the previously disclosed techniques
  • the cocatalysts of the invention may also be used in combination with a t ⁇ (hydrocarbyl)alum ⁇ num compound having from 1 to 10 carbons in each hydrocarbyl group, an oiigome ⁇ c or polymeric alumoxane compound, a d ⁇ (hydrocarbyl)(hydrocarbyloxy)alum ⁇ num compound having from 1 to 10 carbons in each hydrocarbyl or hydrocarbyloxy group, or a mixture of the foregoing compounds, if desired
  • These aluminum compounds are usefully employed for their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture
  • Preferred aluminum compounds include C2-6 tnalkyl aluminum compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, and methylalum
  • Solution polymerization takes place under conditions in which the diluent acts as a solvent for the respective components of the reaction, particularly the EP or EPDM polymer
  • Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures
  • useful solvents include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar ETM, available from Exxon Chemicals Inc , cycloaikanes such as cyclopentane and cyciohexane, and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene
  • the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen Ethylene is added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the ⁇ -olefin and diene monomers.
  • a dry, inert gas such as, for example, nitrogen Ethylene is added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the ⁇ -olefin and diene monomers.
  • the ethylene content of the polymer is determined by the ratio of ethylene differential pressure to the total reactor pressure.
  • the polymerization process is carried out with a differential pressure of ethylene of from about 10 to about 1000 psi (70 to 7000 kPa), most preferably from about 40 to about 400 psi (30 to 300 kPa)
  • the polymerization is generally conducted at a temperature of from 25 to 200°C, preferably from 75 to 170°C, and most preferably from greater than 95 to 140°C.
  • the polymerization may be carried out as a batchwise or a continuous polymerization process.
  • a continuous process is preferred, in which event catalyst, ethylene, ⁇ -olefin. and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom
  • continuous and continuous as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular intervals, so that, over time, the overall process is continuous.
  • one means for carrying out such a polymerization process is as follows: In a stirred-tank reactor propylene monomer is introduced continuously together with solvent, diene monomer and ethylene monomer
  • the reactor contains a liquid phase composed substantially of ethylene, propylene and diene monomers together with any solvent or additional diluent If desired, a small amount of a "H"-branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene or 1 ,9-decad ⁇ ene may also be added.
  • Catalyst and cocatalyst are continuously introduced in the reactor liquid phase.
  • the reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by cooling or heating coils, jackets or both.
  • the polymerization rate is controlled by the rate of catalyst addition.
  • the ethylene content of the polymer product is determined by the ratio of ethylene to propylene in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor.
  • the polymer product molecular weight is controlled. optionally, by controlling other polymerization variables such as the temperature. monomer concentration, or by a stream of hydrogen introduced to the reactor, as is well known in the art.
  • the reactor effluent is contacted with a catalyst kill agent such as water
  • a catalyst kill agent such as water
  • the polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous ethylene and propylene as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devoiatilization in equipment such as a devolati zing extruder
  • the mean residence time of the catalyst and polymer in the reactor generally is from about 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours
  • the polymerization is conducted in a continuous solution polymerization system comprising two reactors connected in series or parallel
  • a relatively high molecular weight product (Mw from 300.000 to 600,000, more preferably 400.000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (Mw 50,000 to 300,000) is formed
  • Mw 50,000 to 300,000 relatively low molecular weight
  • the final product is a blend of the two reactor effluents which are combined prior to devoiatilization to result in a uniform blend of the two polymer products
  • the reactors are connected in series, that is effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen i added to the second reactor Reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is from 20 80 to 80.20
  • the temperature of the second reactor is controlled to produce the lower molecular weight product
  • the process of the present invention can be employed to advantage in the gas phase copolyme ⁇ zation of olefins.
  • Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolyme ⁇ zation of ethylene and propylene, and the copolymerization of ethylene with higher ⁇ -olefins such as, for example, 1 -butene, 1 -hexene, 4-methyl- l -pentene are well known in the art.
  • Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.
  • the gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone.
  • Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate, the tluidization grid, by a flow of fluidization gas.
  • the gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed.
  • the hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream.
  • the gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
  • a preferred method of cooling of the bed is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode.
  • the volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6. carbon atoms.
  • the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect.
  • olefin monomers which can be employed in this manner are olefins containing about three to about eight, preferably three to six carbon atoms.
  • the volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed.
  • the evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop.
  • the recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed.
  • the polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst.
  • catalyst can be supported on an inorganic or organic support material as described above.
  • the catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymer particles.
  • the polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed.
  • Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas. hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode.
  • the produced polymer is discharged continuously or discontinuously from the fluidized bed as desired.
  • the gas phase processes suitable for the practice of this invention are preferably continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor.
  • the fluidized bed of the gas phase process is operated at temperatures greater than 50°C, preferably from about 60°C to about 1 10°C, more preferably from about 70°C to about 1 10°C.
  • the molar ratio of comonomer to monomer used in the polymerization depends upon the desired density for the composition being produced and is about 0 5 or less. Desirably, when producing materials with a density range of from about 0.91 to about 0.93 the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0 01 Typically, the ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably iess than 0.02 and may even be less than 0.01.
  • the catalysts may be used to polymerize ethylemcally and/or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination
  • Preferred monomers include the C2-20 ct-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1 -hexene, 3-methyl-l-pentene, 4-methyl- l -pentene, 1 -octene, 1 -decene, long chain macromolecular ⁇ -olefins, and mixtures thereof
  • the catalysts may also be utilized in combination with at least one additional homogeneous 01 heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties
  • An example of such a process is disclosed in WO 94/00500, equivalent to U S Serial Number 07/904,770, as well as U S Serial Number 08/10958, filed January 29, 1993, the teachings or which are hereby incorporated by reference herein
  • the long chain branch is longer than the short chain branch that results from the incorporation of one or more ⁇ -olefin comonomers into the polymer backbone
  • the empirical effect of the presence of long chain branching in the copolymers of this invention is manifested as enhanced rheological properties which are indicated by higher flow activation energies, and greater L 1 /I 2 than expected from the other structural properties of the compositions
  • highly preferred polyolefin copolymer compositions of this invention have reverse molecular architecture, that is, there is a molecular weight maximum which occurs in that 50 percent by weight of the composition which has the highest weight percent comonomer content.
  • polyolefin copolymer compositions which also have long chain branches along the polymer backbone, especially when produced with a catalyst system of this invention having a single metallocene complex of this invention in a single reactor in a process for the polymerization of an ⁇ -olefin monomer with one or more olefin comonomers, more especially when the process is a continuous process
  • the comonomer content as a function of molecular weight can be measured by coupling a Fourier transform infrared spectrometer (FTIR) to a Waters 150°C Gel Permeation Chromatograph (GPC)
  • FTIR Fourier transform infrared spectrometer
  • GPC Waters 150°C Gel Permeation Chromatograph
  • the comonomer partitioning factor Cpf is calculated from GPC/FTIR data It characterizes the ratio of the average comonomer content of the higher molecular weight fractions to the average comonomer content of the lower molecular weight fractions Higher and lower molecular weight are defined as being above or below the median molecular weight respectively, that is, the molecular weight distribution is divided into two parts of equal weight.
  • c is the mole fraction comonomer content
  • w is the normalized weight fraction as determined by GPC/FTIR for the m FTIR data points below the median molecular weight Only those weight tractions, w, or w, which have associated mole fraction comonomer content values are used to calculate Cp [
  • Cpf desirably is equal to or greater than 1 10, more desirably is equal to ot greater than I 15 even more desirably is equal to or greater than 1 20, preferably is equal to or greater than 1 30 more preferably is equal to or greater than 1 40, even more preferably is equal to or greater than 1 50, and still more preferably is equal to or greater than 1 60
  • ATREF-DV has been described in U S Patent No 4,798.081 , which is hereby incorporated by reference, and in "Determination of Short-Chain Branching Distributions of Ethylene copolymers by Automated Analytical Temperature Rising Elution Fractionation" (Auto-ATREF), J of Appl Pol Sci Applied Polymer Symposium 45, 25-37 (1990)
  • ATREF-DV is a dual detector analytical system that is capable of fractionating semi-crystalline polymers like Linear Low Density Polyethylene (LLDPE) as a function of crystallization temperature while simultaneously estimating the molecular weight of the fractions
  • LLDPE Linear Low Density Polyethylene
  • ATREF-DV is analogous to Temperature Rising Elution Fractionation (TREF) analysis that have been published in the open literature over the past 15 years The primary difference is that this Analytical - TREF (ATREF) technique is done on a small scale and fractions are not actually isolated Instead, a typical liquid chromatographic (LC) mass
  • a commercially available viscometer especially adapted for LC analysis such as a ViskotekTM is coupled with the IR mass detector Together these two LC detectors can be used to calculate the intrinsic viscosity of the ATREF-DV eluant
  • the viscosity average molecular weight of a given fraction can then be estimated using appropriate Mark Houwink constants, the corresponding intrinsic viscosity, and suitable coefficients to estimate the fractions concentration (dl/g) as it passes through the detectors
  • a typical ATREF-DV report will provide the weight fraction polymer and viscosity average molecular weight as a function of elution temperature Mp is then calculated using the equation given
  • the molecular weight partitioning factor M p f is calculated from TREF/DV data It characterizes the ratio of the average molecular weight of the fractions with high comonomer content to the average molecular weight of the fractions with low comonomer content Higher and lower comonomer content are defined as being below or above the median elution temperature of the TREF concentration plot respectively, that is, the TREF data is divided into two parts of equal weight.
  • M p f is calculated from the following equation , where: M, is the viscosity average molecular weight and w, is
  • the normalized weight fraction as determined by ATREF-DV for the n data points in the fractions below the median elution temperature M is the viscosity average molecular weight and w, is the normalized weight fraction as determined by ATREF- DV for the m data points in the fractions above the median elution temperature Only those weight fractions, w, or w, which have associated viscosity average molecular weights greater than zero are used to calculate Mpf For a valid calculation, it is required that n and m are greater than or equal to 3
  • M p f desirably is equal lo or greater than 1 15, more desirably is equal to or greater than 1 30. even more desirably is equal to or greater than 1 40, preferably is equal to or greater than I 50, more preferably is equal to or greater than 1 60, even more preferably is equal to or greater than 1 70
  • Vanan XL-300 (FT 300 MHz, ' H, 75 MHz, ! 3 C) 1 H NMR and 3 C ( ! H ⁇ NMR spectra are referenced to the residual solvent peaks and are reported in ppm relative to tetramethylsilane. All J values are given in Hz. Mass spectra (El) were obtained on the AutoSpecQFDP. 1 -indanone, «-BuL ⁇ , Me2SiCh. NH2-f-Bu, NEt3 and MeMgl were purchased from Aldrich Chemical Co. All compounds were used as received.
  • N2.N2 Dimethyl- 1 -( 1 -(rerr-butylamino)- 1 , 1 -dimethylsilyl)- 1 H-2- ⁇ ndenam ⁇ ne, dilithium salt (3 40 g, 1 1.3 mmol) dissolved in 30 mL of THF was added within 2 minutes to a suspension of TiCl3(THF)3 (4.19 g, 1 1.3 mmol) in 60 mL of THF. After 1 hour of mixing, PbCh (2.04 g, 7 34 mmol) was added as a solid. The reaction mixture was stirred an additional 1.5 hours. The solvent was removed under reduced pressure.
  • a dark purple block-shaped crystal of dimensions 0.21 x 0 17 x 0 06 mm was immersed in oil, Paratone N, Exxon, and mounted on a thin glass fiber
  • the crystal was bathed in a cold nitrogen stream tor the duration of data collection (- 100 C)
  • Three sets of 20 frames each were collected covering three perpendicular sectors of space using the ⁇ scan method and with a ten second exposure time Integration of the frames followed by reflection indexing and least squares refinement produced a crystal orientation matrix and a monclinic lattice
  • the last run (# 5) is the rcmeasurement of the first 50 frames from run numbei 1 This is done to monitor crystal and diffractometer stability and to correct for any crystal decay
  • Diffractometer setup includes a 0 8 mm collimator providing an X-ray beam of 0 8 mm in diameter Generator power was set at 50 KV and 35 mA.
  • Program SMART' was usec j f or diffractometer control, fi me scans, indexing, orientation matrix calculations, least squares refinement of cell parameters, crystal faces measurements and the actual data collection Program ASTRO ' was used to set up data collection strategy
  • the structure was solved by direct methods in SHELXTL5 ⁇ from which the positions of all of the non-H atoms were obtained
  • the structure was refined, also in SHELXTL5, using full-matrix least-squares refinement
  • the non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were located by a Difference Fourier map and refined without any constraints
  • 3639 observed reflections with I > 2s(I) were used to refine 313 parameters and the resulting R ] , WRT and S (goodness of fit) were 2 93 percent, 7 40 percent and
  • the structure was solved by direct methods in SHELXTL5 from which the positions of all of the non-H atoms were obtained
  • the structure was refined, also in SHELXTL5, using full-matrix least-squares refinement
  • the non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were located by a Difference Fourier map and refined without any constraints.
  • 4838 observed reflections with I > 2 ⁇ (I) were used to refine 432 parameters and the resulting R ] , WR2 and S (goodness of fit) were 3.13 percent, 7. 17 percent and 1 .023, respectively.
  • linear absorption coefficient, atomic scattering factors and anomalous- dispersion corrections were calculated from values from the International Tables for X-ray Crystallography International Tables for X-ray Crystallography ( 1974). Vol. IV. p. 55. Birmingham: Kynoch Press. (Present distributor, D. Reidel, Dordrecht.).
  • Figure 1 shows the crystal structure of dichloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dimethy 1- 1 -(( 1 ,2,3,3a,7a- ⁇ )-2-dimethyIamino- 1 H-inden- 1 -yl)silanaminato-(2-)-N-)- titanium.
  • R i A(IIF 0 I - IFcll) / AIF 0 I
  • wR 2 [A[w(Fo 2 - Fc 2 ) 2 ] / A[w(Fo 2 ) 2 ]] 1 /2
  • Rjnt. A IFo 2 - F 0 2 (mean)l 2 / A[F 0 2 ]
  • a translucent, red, platy crystal of ONSiTiCh i 7H25 having approximate dimensions of 0.4 x 0.2 x 0.06 mm was mounted using oil, (Paratone-N, Exxon) on a glass fiber.
  • Ail measurements were made on an Enraf-Nonius CAD4 diffractometer with graphite monochromated Mo-K ⁇ radiation.
  • the intensities of three representative reflection were measured after every 90 minutes of X-ray exposure time. No decay correction was applied.
  • the linear absorption coefficient, ⁇ . for Mo-K ⁇ radiation is 7.7 cm" ' .
  • An analytical absorption correction was applied which resulted in transmission factors ranging from 0.85 to 0.95.
  • the data were corrected for Lorentz and polarization effects.
  • the standard deviation of an observation of unit weight 0 was 1 47
  • the weighting scheme was based on counting statistics. Plots of ⁇ w(
  • Neutral atoms scattering factors were taken from Cromer and Waber (Cromcr. D T. & Waber, J T , "International Tables for X-Ray Crystallography", Vol, IV. The Kynoch Press, Birmingham, England. Table 2.2 A ( 1974)). Anomalous dispersion effects were included in Fcalc (Ibers, J.A. & Hamilton, W C , Acta Crystallogr , 17, 781 ( 1964)); the values for ⁇ f and ⁇ f" were those of Creagh and McAuley (Creagh, D.C. & McAuley, W. J ; "International Tables for Crystallography., Vol C , (A.J.C Wilson, ed.), Kluwer Academic Publishers.
  • Figure 2 shows the crystal structure of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 - a,7a- ⁇ )-2-ethoxy- 1 H-inden- 1 -yl)s ⁇ lanam ⁇ nato-(2-)-N-)-d ⁇ methyl-t ⁇ tan ⁇ um

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Abstract

L'invention concerne des ligands contenant du cyclopentadiényle à hétéroatome substitué, des complexes métalliques contenant lesdits ligands et des systèmes de catalyse à base de composants de catalyse qui comprennent lesdits complexes métalliques. Les complexes métalliques contiennent une liaison hétéroatome-Cp ou une liaison cyclique hétéroatome-Cp en position 2 du Cp. Dans les complexes métalliques préférés, le ligand est un groupe indényle à hétéroatome substitué en position 2. Les systèmes de catalyse pour la polymérisation de l'oléfine peuvent être utilisés à des températures élevées, sont très actifs et permettent de produire un polymère à masse moléculaire élevée.
PCT/US1997/013171 1996-08-08 1997-07-28 Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine WO1998006728A1 (fr)

Priority Applications (9)

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EP97937033A EP1021454A1 (fr) 1996-08-08 1997-07-28 Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine
SK152-99A SK15299A3 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
BR9711115A BR9711115A (pt) 1996-08-08 1997-07-28 Complexo met lico sistema catalisador para polimeriza-Æo de olfina processo para a polimeriza-Æo de olefinas processo de polimeriza-Æo em solu-Æo de alta temperatura produto de poliolefina ligante contendo ciclopentadienila e uso de um ligante
AU39647/97A AU716659B2 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
JP10509760A JP2000516608A (ja) 1996-08-08 1997-07-28 ２―ヘテロ原子置換シクロペンタジエニル含有金属錯体及びオレフィン重合方法
NZ333877A NZ333877A (en) 1996-08-08 1997-07-28 metal complex of a substituted indene derivative and use of the complex in an olefin polymerization process
CA002262377A CA2262377A1 (fr) 1996-08-08 1997-07-28 Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 2 et procede de polymerisation d'olefine
HU9904148A HUP9904148A3 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl containing metal complexes and process for olefin polymerization
NO990546A NO990546L (no) 1996-08-08 1999-02-05 3-heteroatom substituerte cyklopentadienyl-inneholdende metallkomplekser og olefinpolymerisasjonsprosess

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0940408A1 (fr) * 1998-03-04 1999-09-08 Bayer Aktiengesellschaft Composés organo-métalliques
WO2000043406A1 (fr) * 1999-01-25 2000-07-27 Chisso Corporation Composes metallocenes utilises en tant que composants catalysants pour la polymerisation d'olefines
WO2001042315A1 (fr) * 1999-12-10 2001-06-14 Dow Global Technologies Inc. Complexes metalliques groupe 4 substitues, catalyseurs et procede de polymerisation olefinique
WO2001053362A1 (fr) * 2000-01-19 2001-07-26 Borealis Technology Oy Catalyseurs metallocenes comprenant un (des) groupe(s) cyclopentadienyle(s) siloxy substitue monocyclique(s) destines a la polymerisation d'olefines
WO2001053361A1 (fr) * 2000-01-19 2001-07-26 Borealis Technology Oy Catalyseurs de polymerisation d'olefines a geometrie contrainte ligatures au monocyclopentadienyle a substitution siloxy
US6420299B1 (en) 1999-06-04 2002-07-16 Dow Global Technologies Inc. Boron-substituted cyclopentadienes and metal complexes thereof
EP1253158A1 (fr) * 1999-12-10 2002-10-30 Dow Global Technologies Inc. Complexes métalliques du groupe 4 substitués, catalyseurs et procédé de polymérisation d'oléfines
US6555634B1 (en) 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
US6617407B1 (en) 1999-04-29 2003-09-09 The Dow Chemical Company Bis(n,n-dihydrocarbylamino)-substituted cyclopentadienes and metal complexes thereof
WO2003078483A1 (fr) * 2002-03-14 2003-09-25 Dow Global Technologies Inc. Complexes metalliques a substitution indenyle et procede de polymerisation
US6646071B1 (en) 1999-05-13 2003-11-11 The Dow Chemical Company Metal complexes containing bridging heteroatom for olefin-polymerization-process
US6730754B2 (en) 2000-01-18 2004-05-04 Basell Polyolefine Gmbh Process for producing substantially amorphous propylene-based polymers
US6825295B2 (en) 1999-12-10 2004-11-30 Dow Global Technologies Inc. Alkaryl-substituted group 4 metal complexes, catalysts and olefin polymerization process
EP0975644B1 (fr) * 1997-04-14 2005-03-16 Borealis Technology Oy Composes metallocenes substitues destines a des systemes catalyseurs de polymerisation de l'olefine, leurs produits intermediaires et des procedes de production
US6927264B2 (en) 2003-05-28 2005-08-09 Dow Global Technologies Inc. Metal complexes and polymerization process using same
US7141690B2 (en) 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
WO2011017092A1 (fr) 2009-07-28 2011-02-10 Univation Technologies, Llc Procédés de polymérisation utilisant un catalyseur supporté à géométrie contrainte
US9382361B2 (en) 2014-03-21 2016-07-05 Exxonmobil Chemical Patents Inc. Process to produce ethylene propylene copolymers
KR20190038387A (ko) 2017-09-29 2019-04-08 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 인덴계 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
WO2020174346A1 (fr) 2019-02-28 2020-09-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant
KR20200105409A (ko) 2019-02-28 2020-09-07 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
US10773246B2 (en) 2015-01-06 2020-09-15 Scg Chemicals Co., Ltd. SiO2-layered double hydroxide microspheres and methods of making them
US11053269B2 (en) 2016-05-12 2021-07-06 Scg Chemicals Co., Ltd. Unsymmetrical metallocene catalysts and uses thereof
US11993665B2 (en) 2019-09-27 2024-05-28 Lg Chem, Ltd. Hybrid supported catalyst and method of preparing polyolefin using the same

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JP5579859B2 (ja) * 2010-09-15 2014-08-27 株式会社日本触媒 熱潜在性重合開始剤として用い得る組成物
CN102101897B (zh) * 2010-12-24 2013-02-06 上海化工研究院 侧链含杂环的茂金属催化剂及其在烯烃聚合中的应用
KR102010630B1 (ko) * 2016-01-20 2019-08-13 한화토탈 주식회사 올레핀 중합촉매 및 이를 이용한 올레핀 중합방법
CN110612313A (zh) * 2017-03-23 2019-12-24 埃克森美孚化学专利公司 催化剂体系及其制备和使用方法

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EP0975644B1 (fr) * 1997-04-14 2005-03-16 Borealis Technology Oy Composes metallocenes substitues destines a des systemes catalyseurs de polymerisation de l'olefine, leurs produits intermediaires et des procedes de production
US6248912B1 (en) 1998-03-04 2001-06-19 Bayer Aktiengesellschaft Organometallic compounds
EP0940408A1 (fr) * 1998-03-04 1999-09-08 Bayer Aktiengesellschaft Composés organo-métalliques
WO2000043406A1 (fr) * 1999-01-25 2000-07-27 Chisso Corporation Composes metallocenes utilises en tant que composants catalysants pour la polymerisation d'olefines
US6617407B1 (en) 1999-04-29 2003-09-09 The Dow Chemical Company Bis(n,n-dihydrocarbylamino)-substituted cyclopentadienes and metal complexes thereof
US6555634B1 (en) 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
US6646071B1 (en) 1999-05-13 2003-11-11 The Dow Chemical Company Metal complexes containing bridging heteroatom for olefin-polymerization-process
US6420299B1 (en) 1999-06-04 2002-07-16 Dow Global Technologies Inc. Boron-substituted cyclopentadienes and metal complexes thereof
US6825295B2 (en) 1999-12-10 2004-11-30 Dow Global Technologies Inc. Alkaryl-substituted group 4 metal complexes, catalysts and olefin polymerization process
SG120079A1 (en) * 1999-12-10 2006-03-28 Dow Global Technologies Inc Substituted group 4 metal complexes catalysts and olefin polymerization process
EP1253158A1 (fr) * 1999-12-10 2002-10-30 Dow Global Technologies Inc. Complexes métalliques du groupe 4 substitués, catalyseurs et procédé de polymérisation d'oléfines
US6515155B1 (en) * 1999-12-10 2003-02-04 Dow Global Technologies Inc. Substituted group 4 metal complexes, catalysts and olefin polymerization process
WO2001042315A1 (fr) * 1999-12-10 2001-06-14 Dow Global Technologies Inc. Complexes metalliques groupe 4 substitues, catalyseurs et procede de polymerisation olefinique
US6730754B2 (en) 2000-01-18 2004-05-04 Basell Polyolefine Gmbh Process for producing substantially amorphous propylene-based polymers
WO2001053361A1 (fr) * 2000-01-19 2001-07-26 Borealis Technology Oy Catalyseurs de polymerisation d'olefines a geometrie contrainte ligatures au monocyclopentadienyle a substitution siloxy
WO2001053362A1 (fr) * 2000-01-19 2001-07-26 Borealis Technology Oy Catalyseurs metallocenes comprenant un (des) groupe(s) cyclopentadienyle(s) siloxy substitue monocyclique(s) destines a la polymerisation d'olefines
US7141690B2 (en) 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
US7241927B2 (en) 2002-02-08 2007-07-10 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, catalysts for olefin polymerization, and process for production of olefin polymers
US7098356B2 (en) 2002-03-14 2006-08-29 Dow Global Technologies Inc. Substituted indenyl metal complexes and polymerization process
WO2003078483A1 (fr) * 2002-03-14 2003-09-25 Dow Global Technologies Inc. Complexes metalliques a substitution indenyle et procede de polymerisation
US6927264B2 (en) 2003-05-28 2005-08-09 Dow Global Technologies Inc. Metal complexes and polymerization process using same
WO2011017092A1 (fr) 2009-07-28 2011-02-10 Univation Technologies, Llc Procédés de polymérisation utilisant un catalyseur supporté à géométrie contrainte
US9382361B2 (en) 2014-03-21 2016-07-05 Exxonmobil Chemical Patents Inc. Process to produce ethylene propylene copolymers
US10773246B2 (en) 2015-01-06 2020-09-15 Scg Chemicals Co., Ltd. SiO2-layered double hydroxide microspheres and methods of making them
US11643331B2 (en) 2015-01-06 2023-05-09 Scg Chemicals Co., Ltd. SiO2-layered double hydroxide microspheres and methods of making them
US11053269B2 (en) 2016-05-12 2021-07-06 Scg Chemicals Co., Ltd. Unsymmetrical metallocene catalysts and uses thereof
KR20190038387A (ko) 2017-09-29 2019-04-08 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 인덴계 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
WO2020174346A1 (fr) 2019-02-28 2020-09-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant
KR20200105409A (ko) 2019-02-28 2020-09-07 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
US11993665B2 (en) 2019-09-27 2024-05-28 Lg Chem, Ltd. Hybrid supported catalyst and method of preparing polyolefin using the same
US12006378B2 (en) 2019-09-27 2024-06-11 Lg Chem, Ltd. Polyethylene and its chlorinated polyethylene

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AU716659B2 (en) 2000-03-02
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SK15299A3 (en) 2000-03-13
KR20000029853A (ko) 2000-05-25
ZA976998B (en) 1999-02-08
EP1021454A1 (fr) 2000-07-26

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