WO1998011986A1 - Metallocenes for multimetallic polymerization catalysts - Google Patents
Metallocenes for multimetallic polymerization catalysts Download PDFInfo
- Publication number
- WO1998011986A1 WO1998011986A1 PCT/US1997/016518 US9716518W WO9811986A1 WO 1998011986 A1 WO1998011986 A1 WO 1998011986A1 US 9716518 W US9716518 W US 9716518W WO 9811986 A1 WO9811986 A1 WO 9811986A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- alkyl
- substituted
- cyclopentadienyl
- alkylene
- Prior art date
Links
Classifications
-
- 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
- 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 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
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97942539A EP0951354A4 (en) | 1996-09-19 | 1997-09-18 | Metallocenes for multimetallic polymerization catalysts |
CA002266528A CA2266528A1 (en) | 1996-09-19 | 1997-09-18 | Metallocenes for multimetallic polymerization catalysts |
AU44217/97A AU4421797A (en) | 1996-09-19 | 1997-09-18 | Metallocenes for multimetallic polymerization catalysts |
JP51304198A JP2002515927A (en) | 1996-09-19 | 1997-09-18 | Metallocenes for polymetallic polymerization catalysts |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US2693796P | 1996-09-19 | 1996-09-19 | |
US60/026,937 | 1996-09-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998011986A1 true WO1998011986A1 (en) | 1998-03-26 |
Family
ID=21834668
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/016518 WO1998011986A1 (en) | 1996-09-19 | 1997-09-18 | Metallocenes for multimetallic polymerization catalysts |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0951354A4 (en) |
JP (1) | JP2002515927A (en) |
KR (1) | KR20010039507A (en) |
AU (1) | AU4421797A (en) |
CA (1) | CA2266528A1 (en) |
WO (1) | WO1998011986A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100349979B1 (en) * | 1999-11-18 | 2002-08-22 | 삼성전자 주식회사 | Multi-metallic Metallocene Catalysts for Polymerization of Styrene and Method of Polymerization Using the Same |
DE19827557B4 (en) * | 1998-06-20 | 2004-07-08 | Robert Bosch Gmbh | Method for detecting a vehicle crash |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5214173A (en) * | 1991-12-31 | 1993-05-25 | The University Of Iowa Research Foundation | Cyclopentadienyl dicarbollide complexes of titanium, zirconium and hafnium |
EP0366290B1 (en) * | 1988-10-24 | 1994-06-29 | Chisso Corporation | Process for producing olefin polymers |
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 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69419893T2 (en) * | 1993-12-27 | 1999-12-02 | Mitsui Chemicals Inc | Catalyst and process for olefin polymerization |
-
1997
- 1997-09-18 CA CA002266528A patent/CA2266528A1/en not_active Abandoned
- 1997-09-18 KR KR1019997002391A patent/KR20010039507A/en not_active Application Discontinuation
- 1997-09-18 AU AU44217/97A patent/AU4421797A/en not_active Abandoned
- 1997-09-18 EP EP97942539A patent/EP0951354A4/en not_active Withdrawn
- 1997-09-18 JP JP51304198A patent/JP2002515927A/en active Pending
- 1997-09-18 WO PCT/US1997/016518 patent/WO1998011986A1/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0366290B1 (en) * | 1988-10-24 | 1994-06-29 | Chisso Corporation | Process for producing olefin polymers |
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 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0951354A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19827557B4 (en) * | 1998-06-20 | 2004-07-08 | Robert Bosch Gmbh | Method for detecting a vehicle crash |
KR100349979B1 (en) * | 1999-11-18 | 2002-08-22 | 삼성전자 주식회사 | Multi-metallic Metallocene Catalysts for Polymerization of Styrene and Method of Polymerization Using the Same |
Also Published As
Publication number | Publication date |
---|---|
KR20010039507A (en) | 2001-05-15 |
EP0951354A1 (en) | 1999-10-27 |
AU4421797A (en) | 1998-04-14 |
CA2266528A1 (en) | 1998-03-26 |
EP0951354A4 (en) | 2000-08-09 |
JP2002515927A (en) | 2002-05-28 |
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