EP0951354A4 - Metallocenes pour catalyseurs a polymerisation plurimetallique - Google Patents

Metallocenes pour catalyseurs a polymerisation plurimetallique

Info

Publication number
EP0951354A4
EP0951354A4 EP97942539A EP97942539A EP0951354A4 EP 0951354 A4 EP0951354 A4 EP 0951354A4 EP 97942539 A EP97942539 A EP 97942539A EP 97942539 A EP97942539 A EP 97942539A EP 0951354 A4 EP0951354 A4 EP 0951354A4
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
alkyl
substituted
cyclopentadienyl
alkylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97942539A
Other languages
German (de)
English (en)
Other versions
EP0951354A1 (fr
Inventor
Allan Brent Furtek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0951354A1 publication Critical patent/EP0951354A1/fr
Publication of EP0951354A4 publication Critical patent/EP0951354A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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 System
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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

Definitions

  • the invention relates to new metallocene compounds comprising at least two transition metals.
  • Catalysts containing at least two transition metals have been synthesized. These catalysts have been used in olefin polymerization, for example, in ethylene polymerization and copolymerization.
  • the recent literature reports catalysts which have been synthesized to include one or more transition metals, both in the form of metallocene or a combination of metallocene and Ziegler-Natta catalyst.
  • the earlier catalysts containing two transition metals were prepared as physical admixtures, unsupported or supported on a carrier. The interaction between two different sources of transition metal in a single catalyst may affect the ultimate activity and selectivity characteristics of the two transition metals.
  • the invention relates to a composition which is defined by the general formula
  • M is a transition metal moiety and each L is a linkage, each of which may be the same or different as illustrated below; the transition metal moiety M and an atom or molecular moiety generically defined by B are linked via the linking group L to form a star molecule.
  • the subscript r is a number no greater than the valence of B.
  • the molecule containing at least two transition metals may be used as a catalyst composition.
  • the transition metal containing molecule can polymerize ethylene or copolymerize ethylene with a second alpha olefin.
  • the composition When used as a catalyst for olefin polymerization the composition may be used alone or contacted with an alumoxane, and/or monomeric Al(III) compound such as the trialkylaluminum or dialkylaluminum halides or hydrides (in each of which the alkyl is methyl, ethyl, butyl, isobutyl) and/or ionic lewis acid activators such as B(C 6 F 6 ) 3 , [Ph 3 C] + [B(C 6 F 5 ) 4 ].
  • an alumoxane and/or monomeric Al(III) compound
  • the trialkylaluminum or dialkylaluminum halides or hydrides in each of which the alkyl is methyl, ethyl, butyl, isobutyl
  • ionic lewis acid activators such as B(C 6 F 6 ) 3 , [Ph 3 C] + [B(C 6 F 5 ) 4
  • each site is designed to produce a characteristic type of polymer, which differ in molecular weight, molecular weight distribution short chain branching from comonomer incorporation, long chain branching, etc.
  • a polymer product which is multimodal in molecular weight, branching and other properties, may be produced, and since produced by a single catalyst molecule, these different polymer molecules will be blended thoroughly at the molecular level, thus improving the physical properties of the blended polymer product.
  • the invention relates to a composition which is characterized by the empirical formula
  • W is silicon, boron, carbon, or nitrogen and derivations thereof; x, y, z and are numbers which have numerical values less than the valence of W; and m+x+y+z is equal to the valence of W; each of M 1 , M 2 , M 3 and M 4 is the same or different and is Mex x 3 , wherein Me is a Group IV or V transition metal, preferably hafnium, zirconium or titanium and X 1 , X 2 and X 3 may be the same or different and each is independently a halide (iodide, bromide, chloride or fluoride) ; alkyl of 1 to 6 carbon atoms; or Cp wherein Cp is unsubstituted cyclopentadienyl or cyclopentadienyl substituted with one or more alkyl groups of 1 to 6 carbon atoms straight or branched chain, or saturated or unsaturated alkylene of 1 to 8 carbon atoms, which
  • aryl phenyl or benzyl
  • W is silicon, boron, nitrogen or carbon, and compounds, including organic derivatives, thereof.
  • the composition may be used alone or with a support as a catalyst. Accordingly, unsupported and supported catalysts can be made in accordance with the invention.
  • the carrier or support used interchangeably herein, is selected from the group consisting of silica, alumina or silica/ alumina.
  • the silica bears OH (hydroxyl) groups. As a result of its hydroxyl content the compound may become bound to the carrier via reaction or bonding of W with surface hydroxyl group.
  • the composition may be used as a catalyst, with or without an activator.
  • compositions may be synthesized by various methods.
  • the method of synthesis of compounds in which at least two of the group comprising L 1 , L 2 , L 3 and L 4 is cyclopentadienyl unsubstituted or substituted can be prepared as follows: unsubstituted cyclopentadiene or substituted derivatives thereof, which contain acidic hydrogens on the ring itself are contacted with sodium or butyl lithium to form the alkali metal salt of the unsubstituted or substituted cyclopentadiene. Formation of the alkali metal salt may be undertaken in a suitable solvent, for example, ether or hydrocarbon solvents, at temperatures from -78 °C to +30 "C. The salt may be isolated.
  • a suitable solvent for example, ether or hydrocarbon solvents
  • the alkali metal salt can be contacted with trichloromethylsilane (MeSiCl 3 ) , in a molar ratio of of at least three (3) moles of alkali metal salt to one mole, of silane to form a triscylopentadienyl compound, e.g. tris (cyclopentadienyl) -methyl-silane.
  • trichloromethylsilane MeSiCl 3
  • silane compound in which the precursor chloro groups (of the trichloromethylsilane) have been replaced by cyclopentadienyl groups may then be deprotonated by reaction with one, two, three or more equivalents of a suitable base, for example butyl lithium, then contacted with one or more transition metal salts.
  • the salts of the transition metal can be the halides (chlorine or bromine, e.g. TiCl 4 or ZrCl 4 ) .
  • the transition metal salts can be halide or alkyl transition metal salts consisting at least one cyclopentadienyl group, unsubstituted or substituted with alkyl of 1 to 6 carbon atoms or alkylene groups of l to 6 carbon atoms. Separation of the desired compound is via recrystallization, sublimation or other suitable means.
  • the transition metals of the transitipn metal salt can be zirconium, hafnium or titanium, and admixtures thereof.
  • the group is an unsubstituted, a mono- or a polysubstituted cyclopentadienyl group.
  • the substituents on the cyclopentadienyl group can be preferably straight-chain cr branched Cj-C 6 alkyl groups.
  • the cyclopentadienyl group can be also a part of a bicyclic or a tricyclic moiety such as indenyl, tetrahydroindenyl , fluorenyl or a partially hydrogenated fluorenyl group, as well as a part of a substituted bicyclic or tricyclic moiety, and each of X 1 , X 2 and X 3 may be the same or different.
  • the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilane groups, such as -CH 2 -, -CH 2 -CH 2 -, -CR'R"- and -CR , R H -CR'R"- where R' and R" are short alkyl groups or hydrogen,
  • alkyl groups are preferably straight-chain or branched C ⁇ Cg alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl or n-octyl.
  • Suitable cyclopentadienyl groups include indenyl cyclopentadienyl , pentamethylcyclopentadienyl , n-butylcyclopentadienyl , iso-butylcyclopentadienyl , dimethylcyclopentadienyle, indenyl) , 4 , 5, 6,7-tetrahydro-l- indenyl) and ethylene-(bis(4,5,6,7-tetrahydro-l-indenyl) )
  • the ethylene resin, homopolymer or copolymer, produced in the presence of a composition containing or derived from (M 1 a L 1 b ) x (M 2 c L 2 d ) y (M 3 e L 3 f ) 2 W(M 4 g L 4 h ) B will contain residues of that composition. It will contain 0.01 to 4500 ppm transition metals (provided by M 1 , M 2 , M 3 and M 4 ) .
  • Copolymers of ethylene will contain as a comonomer at least one olefin which contains 3 to 10 carbcn atoms, preferably 1-butene, 1-hexene or 1-octene.
  • the olefin polymerization may be undertaken in solution, slurry or gas phase.
  • ethylene polymerization or copolymerization of ethylene with an alpha olefin of 3 to 10 carbon atoms is undertaken in the gas phase, for example, in a fluid bed, it is essential to operate the fluid bed reactor at a temperature below the sintering temperature of the polymer particles. To insure that sintering will not occur, operating temperatures below the sintering temperature are desired.
  • an operating temperature of 60° to 115°C is preferred, and a temperature of 75° to 95°C is most preferred.
  • the fluid bed reactor is operated at pressures of about 150 to 350 psig, with operation at the higher pressures in such ranges favoring heat transfer since an increase in pressure increases the unit volume heat capacity of the gas.
  • a "diluent" gas may be employed in the polymerizations. It is nonreactive under the conditions in the polymerization reactor.
  • the diluent gas can be nitrogen, argon, helium, methane, ethane, and the like.
  • the superficial gas velocity of the gaseous reaction mixture through the bed must exceed the minimum flow required fpr fluidizatipn, and preferably is at least 0.2 feet per seccnd above the minimum flow. Ordinarily the superficial gas velocity does not exceed 5.0 feet per second, and most usually no more than 2.5 feet per second is sufficient.
  • the feed stream of gaseous monomer, with or without inert gaseous diluents, is fed into the reactor which operates at a space time yield of about 2 to 20 pounds/hour/cubic foot of bed volume.
  • the products may contain any of various additives conventionally added to polymer compositions such as lubricants, microtalc, stabilizer, antioxidants, compatibilizers, pigments, etc. These reagents can be employed to stabilize the products against oxidation.
  • additive packages comprising 400-1200 ppm hindered phenol (s); 700-2000 ppm phosphites; 250-1000 ppm antistats and 250-1000 ppm stearates, for addition to the resin powders, can be used for pelletization.
  • the polymers can be added directly to a blown film extruder, e.g., a Sterling extruder, to produce films having a thickness of about 0.5 TO 5 mils.
  • the resins produced using the multimetallic catalysts described here may also be used for many other purposes, for example, blow molding, injection molding or rotomolding applications.
  • the sites of the multimetallic catalysts to produce polymer molecules with desired properties (e.g., molecular weight, molecular weight distribution, short chain or long chain branching from comonomer, etc.) the type of resins produced by the catalyst may be tailored for specific uses. This would provide a significant advantage over the current technology.

Abstract

La présente invention concerne de nouveaux composés de métallocène contenant au moins deux métaux de transition.
EP97942539A 1996-09-19 1997-09-18 Metallocenes pour catalyseurs a polymerisation plurimetallique Withdrawn EP0951354A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US2693796P 1996-09-19 1996-09-19
US26937P 1996-09-19
PCT/US1997/016518 WO1998011986A1 (fr) 1996-09-19 1997-09-18 Metallocenes pour catalyseurs a polymerisation plurimetallique

Publications (2)

Publication Number Publication Date
EP0951354A1 EP0951354A1 (fr) 1999-10-27
EP0951354A4 true EP0951354A4 (fr) 2000-08-09

Family

ID=21834668

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97942539A Withdrawn EP0951354A4 (fr) 1996-09-19 1997-09-18 Metallocenes pour catalyseurs a polymerisation plurimetallique

Country Status (6)

Country Link
EP (1) EP0951354A4 (fr)
JP (1) JP2002515927A (fr)
KR (1) KR20010039507A (fr)
AU (1) AU4421797A (fr)
CA (1) CA2266528A1 (fr)
WO (1) WO1998011986A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19827557B4 (de) * 1998-06-20 2004-07-08 Robert Bosch Gmbh Verfahren zum Erkennen eines Fahrzeug-Crashes
KR100349979B1 (ko) * 1999-11-18 2002-08-22 삼성전자 주식회사 스티렌계 중합용 다중금속 메탈로센 촉매 및 이를 이용한스티렌계 중합체의 제조방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0664304A2 (fr) * 1993-12-27 1995-07-26 Mitsui Petrochemical Industries, Ltd. Catalyseur et procédé pour la polymérisation d'oléfines

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2835729B2 (ja) * 1988-10-24 1998-12-14 チッソ株式会社 オレフィン重合体の製造方法
US5214173A (en) * 1991-12-31 1993-05-25 The University Of Iowa Research Foundation Cyclopentadienyl dicarbollide complexes of titanium, zirconium and hafnium
US5372980A (en) * 1993-06-03 1994-12-13 Polysar Bimetallic metallocene alumoxane catalyst system and its use in the preparation of ethylene-alpha olefin and ethylene-alpha olefin-non-conjugated diolefin elastomers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0664304A2 (fr) * 1993-12-27 1995-07-26 Mitsui Petrochemical Industries, Ltd. Catalyseur et procédé pour la polymérisation d'oléfines

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DIAMOND, GARY M. ET AL: "New mono- and bi-nuclear ansa-metallocenes of zirconium and hafnium as catalysts for the polymerization of ethene and propene", J. CHEM. SOC., DALTON TRANS. ( 1996 ), (6), 921-38, XP000914569 *
See also references of WO9811986A1 *
USHIODA, TSUTOMU ET AL: "Synthesis and catalytic properties of ansa-binuclear metallocenes of the Group IV transition metals", J. ORGANOMET. CHEM. ( 1996 ), 518(1-2), 155-166, XP004035869 *

Also Published As

Publication number Publication date
CA2266528A1 (fr) 1998-03-26
AU4421797A (en) 1998-04-14
EP0951354A1 (fr) 1999-10-27
KR20010039507A (ko) 2001-05-15
JP2002515927A (ja) 2002-05-28
WO1998011986A1 (fr) 1998-03-26

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