CA2175968A1 - Organometallic compound - Google Patents
Organometallic compoundInfo
- Publication number
- CA2175968A1 CA2175968A1 CA002175968A CA2175968A CA2175968A1 CA 2175968 A1 CA2175968 A1 CA 2175968A1 CA 002175968 A CA002175968 A CA 002175968A CA 2175968 A CA2175968 A CA 2175968A CA 2175968 A1 CA2175968 A1 CA 2175968A1
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- Prior art keywords
- organometallic compound
- molybdenum
- ligand
- tert
- bis
- Prior art date
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/61927—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- 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
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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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
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Organometallic compound The invention relates to an organometallic compound of the formula I
(?) where M is chromium, molybdenum or tungsten, L is a ?
ligand, T is a bridge, A is a ? ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen. The organometallic compound is suitable as a catalyst component for olefin polymerization.
(?) where M is chromium, molybdenum or tungsten, L is a ?
ligand, T is a bridge, A is a ? ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen. The organometallic compound is suitable as a catalyst component for olefin polymerization.
Description
HOECHST AKTIENGESELLSCHAFT HOE 95/F 088 Dr.SK/St DESCRIPTION
Organometallic compound The present invention relates to an organometallic compound which can be used very advantageously aæ a catalyst component, e.g. for the preparation of polyolefins or metathesis for ring-opening polymerization (ROMP). Metallocenes and semi-sandwich complexes are not only of great interest for polymerization, oligomerization or metathesis of olefins, but can also be used as hydrogenation, epoxidation, isomerization and C-C
coupling catalysts (Chem. Rev. 1992, 92, 965-994).
Organometallic compounds containing Cr, Mo or W and having ~ ligands can be used as polymerization catalysts (WO 94/11410). However, the preparation of such compounds proves to be difficult.
It is an object of the invention to provide a new organometallic compound which is suitable for olefin polymerization. It has surprisingly been found that a new organometallic compound is obtained directly by reacting a metal tetramide of the 6th transition group of the Periodic Table of the Elements (Cr, Mo, W) with a ligand system without addition of a base such as butyllithium.
The present invention accordingly provides an organometallic compound of the formula I
/ L ~ ~ N R 1 2 T~ ~ ~ ( I ) where M is chromium, molybdenum or tungsten, L is a ~
ligand, T is a bridge, A is a ~ ligand or another electron donor and Rl are, independently of one another, identical or different Cl-C20-hydrocarbon radicals or hydrogen.
L is preferably a substituted or unsubstituted cyclopentadienyl group, T i8 preferably [R22B] n' where B
is carbon, silicon, germanium or tin and the radicals R2 are identical or different and are each hydrogen or a Cl-C30-hydrocarbon radical such as Cl-C10-alkyl or C6-Cl4-aryl, and n is equal to 1, 2, 3 or 4. A is a ~ ligand such as a substituted or unsubstituted cyclopentadienyl group or another electron donor such as 0, PR3, S or NR3, where R3 is hydrogen or a Cl-C30-hydrocarbon radical such as cl-clO-alkyl or C6-Cl4-arYl Rl are preferably identical and are each hydrogen or a Cl-C20-hydrocarbon radical such as Cl-C10-alkyl or C6-Cl6-aryl.
Examples of substituted cyclopentadienyl groups are:
tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopenta-dienyl, isopropylcyclopentadienyl, dimethylcyclopenta-dienyl, trimethylcyclopentadienyl, trimethylethylcyclo-pentadienyl, 5-phenylcyclopentadienyl, diphenylcyclo-pentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilyl-indenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenyl-indenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-iso-propylindenyl, benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-~-acenaphthindenyl, 2-methyl-4,6-diisopropyl-indenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Examples of preferred bridges T are:
dimethylsilanediyl, methylphenylsilanediyl,diphenylsilanediyl,dimethylgermanediyl,l,2-tetramethyl-disilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene, 1,3-propylidene, 1,4-butylidene.
Examples of preferred structural elements A are:
tert-butylamido, cyclohexylamido, phenylamido, 2,6-diisopropylphenylamido, 2,6-di-tert-butylphenylamido, cyclododecylamido, -0-, cyclopentadienyl, indenyl, fluorenyl,cyclopentadienyl,tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopenta-dienyl, tert-butylcyclopentadienyl, isopropylcyclopenta-dienyl, dimethylcyclopentadienyl, trimethylcyclopenta-dienyl, trimethylethylcyclopentadienyl, phenylcyclo-pentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-pnenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-iso-propylindenyl, benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-~-acenaphthindenyl, 2-methyl-4,6-diisopropyl-indenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Examples of particularly preferred organometallic compounds of the formula I are:
bis(dimethylamido){[(tert-butylamido)dimethyl-silyl]cyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)diphenylsilyl]cyclo-pentadienyl}molybdenum,bis(dimethylamido){[(tert-butylamido)ethylidene]cyclo-pentadienyl}molybdenum, bis (dimethylamido){ [(tert-butylamido) i 8 0 -propylidene]cyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethyl-silyl]methylcyclopentadienyl}molybdenum, bis(dimethylamido){ [(tert-butylamido)iso-propylidene]methylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethylsilyl]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)diphenylsilyl]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)ethylidene]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)isopropylidene]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethyl-8ilyl] indenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)diphenyl-0 8ilyl] indenyl}molybdenum,bis(dimethylamido){[(tert-butylamido)ethylidene]indenyl}-molybdenum, bis(dimethylamido){[(tert-butylamido)ethylidene]indenyl}-molybdenum, bis(dimethylamido){[(tert-butylamido)dimethylsilyl]2-methyl-4-phenylindenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethylsilyl]2-methyl-4,5-benzoindenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethyl-8 i lyl ] fluorenyl}molybdenum,bis(dimethylamido){[(tert-butylamido)ethylidene]-fluorenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)isopropylidene]-fluorenyl}molybdenum, bis(dimethylamido){[(phenylamido)dimethylsilyl]cyclop-entadienyl}molybdenum, bis(dimethylamido){[(phenylamido)dimethylsilyl]methylcyc-lopentadienyl}molybdenum, bis(dimethylamido){[(phenylamido)dimethylsilyl]tert-butylcyclopentadienyl}molybdenum,bis(dimethylamido){[(phenylamido)diphenyl-silyl]indenyl}-molybdenum, bis(dimethylamido){[(cyclohexylamido)dimethylsilyl]cyclo-pentadienyl}molybdenum, bis(dimethylamido){[(cyclohexylamido)isopropylidene]meth-ylcyclopentadienyl}molybdenum, bis(dimethylamido){t(cyclohexylamido)dimethylsilyl]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(cyclohexylamido)isopropylidene]-~17~968 indenyl}molybdenum,bis(dimethylamido){[(cyclohexylamido)dimethyl~ilyl]fluor-enyl}molybdenum, bis(dimethylamido)[bis(cyclopentadienyl)isopropylidene]-molybdenum,bis(dimethylamido)[(cyclopentadienyl)(indenyl)isoprop-ylidene]molybdenum, bis(dimethylamido)[(cyclopentadienyl)(fluorenyl)isoprop-ylidene]molybdenum.
The present invention also provides a process for preparing an organometallic compound of the formula I, which comprises reacting a compound of the formula II, where L is a ~ ligand, T is a bridge and A is a ~ ligand or another electron donor, with a compound of the formula III, where M is chromium, molybdenum or tungsten and are, independently of one another, identical or different Cl-C20-hydrocarbon radicals such as C1-C10-alkyl or C6-Cl4-aryl or hydrogen.
L H
/
T~ ( I I ) ~(NR 2)~ ( I I I ) AH
The reaction is preferably carried out in an aprotic solvent, e.g. ether. The temperature can be between -78 and 140C, preferably from 0 to 40C. The compound of the formula II and the compound of the formula III are preferably used in equimolar amounts. The compound of the formula III can also be used in excess, since unreacted metal amide of the formula III can easily be removed by sublimation.
The methods of preparing compounds of the formula II are known (Chem. Ber. 1990, 123, 1649). The methods of preparing compounds of the formula III are likewise known (J. Chem. Soc. A, (1971), 2741).
Organometallic compounds of the formula I are, in combination with a cocatalyst, suitable catalysts for the polymerization of olefins for preparing olefin polymers.
The present invention thus also provides a process for preparing a polyolefin by polymerization of at least one olefin in the presence of a catalyst, wherein the catalyst comprises at least one organometallic compound of the formula I and at least one cocatalyst. The polymerization can be a homopolymerization or a copolymerization.
Preference is given to homopolymerizing or copolymerizing olefins of the formula Ra-CH=CH-Rb, where Ra and Rb are identical or different and are each a hydrogen atom or a hydrocarbon radical having from 1 to 20 carbon atoms, in particular from 1 to 10 carbon atoms, or Ra and Rb together with the atoms connecting them form one or more rings. Examples of such olefins are 1-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene or 1,4-h~YA~iene and cyclic olefins such as norbornene, tetracyclododecene, norbornadiene or vinylnorbornene. In the process of the invention, preference is given to homopolymerizing ethylene or propylene, or copolymerizing ethylene with one or more 1-olefins having 3-20 carbon atoms, for example propylene, and/or one or more dienes having 4-20 carbon atoms, for example 1,4-butadiene. Examples of such copolymers are ethylene-propylene copolymers and ethylene-propylene-1,4-hexadiene copolymers.
The polymerization is preferably carried out at a temperature of from -60 to 250C, particularly preferably from 50 to 200C. The pressure is preferably from 0.5 to 2000 bar, particularly preferably from 5 to 64 bar.
The polymerization can be carried out in ~olution, in bulk, in suspension or in the gas phase, continuously or 21759~;8 batchwise, and in one or more stages. A preferred embodiment is gas-phase polymerization.
The catalyst used in the process of the invention preferably comprises one organometallic compound of the formula I. It is also possible to use mixtures of two or more organometallic compounds of the formula I, or mixtures of organometallic compounds of the formula I
with other metallocenes, semi-sandwich compounds or classic Ziegler-Natta catalysts, e.g. for preparing polyolefins having a broad or multimodal molecular weight distribution.
In principle, a suitable cocatalyst in the process of the invention is any compound which, owing to its ~ewis acidity, can convert the neutral metallocene into a cation and stabilize the latter ("labile coordination").
Furthermore, the cocatalyst or the anion formed therefrom should undergo no further reactions with the metallocene cation formed (EP 427 697). As cocatalyst, preference is given to using an aluminium compound and/or a boron compound.
The boron compound preferably has the formula R5XNH4 XBR64, R5XPH4 xBR64, R53CBR64 or BR63, where x is a number from 1 to 4, preferably 3, the radicals R5 are identical or different, preferably identical, and are C1-C1O-alkyl or C6-C18-aryl, or two radicals R5 together with the atoms connecting them form a ring, and the radicals R6 are identical or different, preferably identical, and are C6-Cl8-aryl which can be substituted by alkyl, haloalkyl or fluorine. In particular, R5 is ethyl, propyl, butyl or phenyl and R6 is phenyl, pentafluorophenyl, 3,5-bistri-fluoromethylphenyl, mesityl, xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).
The cocatalyst used is preferably an aluminium compound such as all ;nox~ne and/or an aluminium alkyl.
~17~968 The cocatalyst used i8 particularly preferably an aluminoxane, in particular of the formula IIa for the linear type and/or the formula IIb for the cyclic type, R~ R4 R~
/ A I--O--A I ~ A I \ ( I V a ) R4 _ _p R~
A I O-- ( I Vb) -- p+2 where, in the formulae IVa and IVb, the radicals R4 are identical or different and are each hydrogen or a C1-C20-hydrocarbon group such as a C1-Cl8-alkyl group, a C6-Cl8-aryl group or benzyl, and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R4 are preferably identical and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals R4 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably being present in a proportion of from 0.01 to 40 % (of the radicals R4).
Methods of preparing the aluminoxanes are known (DE 4 004 477).
The exact spatial structure of the al~m;no~nes iæ not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings are joined to g form larger two-~;mensional or three-dimensional structures.
Regardless of the method of preparation, all alum;noYAne solutions have in common a varying content of unreacted aluminium starting compound, which i8 present in free form or as adduct.
It is possible to preactivate the organometallic compound of the invention prior to use in the polymerization reaction by means of a cocatalyst, in particular an aluminoxane. This significantly increases the polymerization activity. The preactivation of the organometallic compound is preferably carried out in solution. For this purpose, the organometallic compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Preference is given to using toluene.
The concentration of the alum;~oYAne in the solution is in the range from about 1 % by weight to the saturation limit, preferably from 5 to 30 % by weight, in each case based on the total amount of solution. The metallocene can be used in the same concentration, but i8 preferably used in an amount of 10-4-1 mol per mol of aluminoxane.
The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The preactivation is carried out at a temperature of from -78 to 100C, preferably from 0 to 70C.
Here, the organometallic compound is preferably used in a concentration, based on the transition metal, of from 10-3 to 10- mol, preferably from 10-4 to 10-7 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. The alum;no~Ane is preferably used in a concentration of from 10-6 to 10~1 mol, preferably from 10-5 to 10 -2 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the organometallic compound. However, higher concentrations are also possible in principle.
To remove catalyst poisons present in the olefin, purification using an aluminium compound, preferably an aluminium alkyl such as trimethylaluminium or triethylaluminium, is advantageous. This purification can be carried out either in the polymerization system itself, or the olefin is, prior to addition to the polymerization system, brought into contact with the aluminium compound and subsequently separated off again.
As molecular weight regulator and/or for increasing the activity, it is possible to add hydrogen in the process of the invention. This enables low molecular weight polyolefins such as waxes to be obtained.
In the process of the invention, the organometallic compound is preferably reacted with the cocata yst outside the polymerization reactor in a separate step using a suitable solvent. Application to a support can be carried out during this step.
A prepolymerization can be carried out in the process of the invention by means of the organometallic compound.
For the prepolymerization, preference is given to using the (or one of the) olefin(s) used in the polymerization.
The catalyst used in the process of the invention can be supported. The application to a support allows, for example, the particle morphology of the polyolefin prepared to be controlled. Here, the organometallic compound can be reacted first with the support and subsequently with the cocatalyst. However, the cocatalyst can also first be supported and subsequently reacted with the organometallic compound. It is also possible to support the reaction product of organometallic compound and cocatalyst. Suitable support materials are, for ~175968 example, silica gels, aluminium oxides, sol d alum;noxAne or other inorganic support materials such as magnesium chloride. Another suitable support material is a polyolefin powder in finely divided form. The preparation of the supported cocatalyst can be carried out, for example, as described in EP 567 952.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent customary for the Ziegler low-pressure process is used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples which may be mentioned are propane, butane, hexane, heptane, isooctane, cyclohexane, methylcycloheYAne. A petroleum or hydrogenated diesel oil fraction can also be used. It is also possible to use toluene. The polymerization is preferably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in in gaseous or liquid form.
The polymerization time can be any desired, since the catalyst system to be used in the process of the invention has only a slight time-dependent decrease in the polymerization activity.
The polymers prepared by the process of the invention are suitable, in particular, for producing shaped bodies such as films, plates or large hollow bodies (e.g. pipes).
The examples below illustrate the invention:
All glass apparatus was baked out in vacuo and flushed with argon. All operations were carried out with exclusion of moisture and oxygen in Schlenk vessels. The solvents used were distilled under argon from an Na/K
~lloy.
1. Bis(dimethylamido){[(phenylamido)dimethyl-~17~968 silyl]cyclopentadienyl}molybdenum 1:
Mo(N(cH3)2)4 (200 mg, 0.74 mmol) i8 dissolved in 10 ml of Et20 and the violet solution is cooled to -78C.
Dimethyl(cyclopentadienyl)(aminophenyl)silane (158 mg, 0.74 mmol) dissolved in 15 ml of Et20 is slowly added.
The reaction mixture is slowly warmed to room temperature and is stirred overnight at this temperature. The dark red solution is heated under reflux for 2 hours, subsequently filtered and the solvent is removed under reduced pressure. Pentane (about 1 ml) is added and the solution is recrystallized at -78C. 160 mg (60 % yield) of a brown solid are isolated.
lH-NMR (400 MHz, C6D6, 25C, TMS): ~ = 0.25 (8, 6H;
Si(CH3)2), 3.20 (8, 12H; N(CH3)2), 4.88 (t, 2H, 3J(H,H) =
2.1 Hz, C5H4), 6.04 (t, 2H, 3J(H,H) = 2.1 Hz, C5H4), 6.84 (t, lH, 3J(H,H) = 7.1 Hz, para-c6H5)~ 7.07 (d, 2H, 3J(H,H) = 8.6 Hz, ortho-C6H5), 7.23 (t, 2H, 3J(H,H) = 8.0 Hz, meta-C6H5).
2. Bis(dimethylamido){[(tert-butylamido)dimethyl-silyl]indenyl}molybdenum 2:
The preparation is carried out by a method similar to Example 1.
lH-NMR (400 MHz, C6D6, 25C, TMS): ~ = 0.28 (8, 6H;
Si(CH3)2), 1.14 (8, 9H; C(CH3)3), 3.26 (8, 12H; N(CH3)2), 4,79 (d, lH, 3J(H,H) = 2.5 Hz, CgH6)~ 6.06 (d, lH, 3J(H,H) = 2.5 Hz, CgH6)~ 6.87 (t, lH, 3J(H,H) = 7.0 Hz, CgH6)~
6.95 (t, lH, 3J(H,H) = 7.2 Hz, CgH6)~ 7.27 (d, lH, 3J(H,H) = 7.9 Hz, C9H6), 7.65 (d, lH, 3J(H,H) = 7.9 Hz, CgH6)~
Organometallic compound The present invention relates to an organometallic compound which can be used very advantageously aæ a catalyst component, e.g. for the preparation of polyolefins or metathesis for ring-opening polymerization (ROMP). Metallocenes and semi-sandwich complexes are not only of great interest for polymerization, oligomerization or metathesis of olefins, but can also be used as hydrogenation, epoxidation, isomerization and C-C
coupling catalysts (Chem. Rev. 1992, 92, 965-994).
Organometallic compounds containing Cr, Mo or W and having ~ ligands can be used as polymerization catalysts (WO 94/11410). However, the preparation of such compounds proves to be difficult.
It is an object of the invention to provide a new organometallic compound which is suitable for olefin polymerization. It has surprisingly been found that a new organometallic compound is obtained directly by reacting a metal tetramide of the 6th transition group of the Periodic Table of the Elements (Cr, Mo, W) with a ligand system without addition of a base such as butyllithium.
The present invention accordingly provides an organometallic compound of the formula I
/ L ~ ~ N R 1 2 T~ ~ ~ ( I ) where M is chromium, molybdenum or tungsten, L is a ~
ligand, T is a bridge, A is a ~ ligand or another electron donor and Rl are, independently of one another, identical or different Cl-C20-hydrocarbon radicals or hydrogen.
L is preferably a substituted or unsubstituted cyclopentadienyl group, T i8 preferably [R22B] n' where B
is carbon, silicon, germanium or tin and the radicals R2 are identical or different and are each hydrogen or a Cl-C30-hydrocarbon radical such as Cl-C10-alkyl or C6-Cl4-aryl, and n is equal to 1, 2, 3 or 4. A is a ~ ligand such as a substituted or unsubstituted cyclopentadienyl group or another electron donor such as 0, PR3, S or NR3, where R3 is hydrogen or a Cl-C30-hydrocarbon radical such as cl-clO-alkyl or C6-Cl4-arYl Rl are preferably identical and are each hydrogen or a Cl-C20-hydrocarbon radical such as Cl-C10-alkyl or C6-Cl6-aryl.
Examples of substituted cyclopentadienyl groups are:
tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopenta-dienyl, isopropylcyclopentadienyl, dimethylcyclopenta-dienyl, trimethylcyclopentadienyl, trimethylethylcyclo-pentadienyl, 5-phenylcyclopentadienyl, diphenylcyclo-pentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilyl-indenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenyl-indenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-iso-propylindenyl, benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-~-acenaphthindenyl, 2-methyl-4,6-diisopropyl-indenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Examples of preferred bridges T are:
dimethylsilanediyl, methylphenylsilanediyl,diphenylsilanediyl,dimethylgermanediyl,l,2-tetramethyl-disilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene, 1,3-propylidene, 1,4-butylidene.
Examples of preferred structural elements A are:
tert-butylamido, cyclohexylamido, phenylamido, 2,6-diisopropylphenylamido, 2,6-di-tert-butylphenylamido, cyclododecylamido, -0-, cyclopentadienyl, indenyl, fluorenyl,cyclopentadienyl,tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopenta-dienyl, tert-butylcyclopentadienyl, isopropylcyclopenta-dienyl, dimethylcyclopentadienyl, trimethylcyclopenta-dienyl, trimethylethylcyclopentadienyl, phenylcyclo-pentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-pnenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-iso-propylindenyl, benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-~-acenaphthindenyl, 2-methyl-4,6-diisopropyl-indenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
Examples of particularly preferred organometallic compounds of the formula I are:
bis(dimethylamido){[(tert-butylamido)dimethyl-silyl]cyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)diphenylsilyl]cyclo-pentadienyl}molybdenum,bis(dimethylamido){[(tert-butylamido)ethylidene]cyclo-pentadienyl}molybdenum, bis (dimethylamido){ [(tert-butylamido) i 8 0 -propylidene]cyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethyl-silyl]methylcyclopentadienyl}molybdenum, bis(dimethylamido){ [(tert-butylamido)iso-propylidene]methylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethylsilyl]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)diphenylsilyl]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)ethylidene]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)isopropylidene]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethyl-8ilyl] indenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)diphenyl-0 8ilyl] indenyl}molybdenum,bis(dimethylamido){[(tert-butylamido)ethylidene]indenyl}-molybdenum, bis(dimethylamido){[(tert-butylamido)ethylidene]indenyl}-molybdenum, bis(dimethylamido){[(tert-butylamido)dimethylsilyl]2-methyl-4-phenylindenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethylsilyl]2-methyl-4,5-benzoindenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)dimethyl-8 i lyl ] fluorenyl}molybdenum,bis(dimethylamido){[(tert-butylamido)ethylidene]-fluorenyl}molybdenum, bis(dimethylamido){[(tert-butylamido)isopropylidene]-fluorenyl}molybdenum, bis(dimethylamido){[(phenylamido)dimethylsilyl]cyclop-entadienyl}molybdenum, bis(dimethylamido){[(phenylamido)dimethylsilyl]methylcyc-lopentadienyl}molybdenum, bis(dimethylamido){[(phenylamido)dimethylsilyl]tert-butylcyclopentadienyl}molybdenum,bis(dimethylamido){[(phenylamido)diphenyl-silyl]indenyl}-molybdenum, bis(dimethylamido){[(cyclohexylamido)dimethylsilyl]cyclo-pentadienyl}molybdenum, bis(dimethylamido){[(cyclohexylamido)isopropylidene]meth-ylcyclopentadienyl}molybdenum, bis(dimethylamido){t(cyclohexylamido)dimethylsilyl]tert-butylcyclopentadienyl}molybdenum, bis(dimethylamido){[(cyclohexylamido)isopropylidene]-~17~968 indenyl}molybdenum,bis(dimethylamido){[(cyclohexylamido)dimethyl~ilyl]fluor-enyl}molybdenum, bis(dimethylamido)[bis(cyclopentadienyl)isopropylidene]-molybdenum,bis(dimethylamido)[(cyclopentadienyl)(indenyl)isoprop-ylidene]molybdenum, bis(dimethylamido)[(cyclopentadienyl)(fluorenyl)isoprop-ylidene]molybdenum.
The present invention also provides a process for preparing an organometallic compound of the formula I, which comprises reacting a compound of the formula II, where L is a ~ ligand, T is a bridge and A is a ~ ligand or another electron donor, with a compound of the formula III, where M is chromium, molybdenum or tungsten and are, independently of one another, identical or different Cl-C20-hydrocarbon radicals such as C1-C10-alkyl or C6-Cl4-aryl or hydrogen.
L H
/
T~ ( I I ) ~(NR 2)~ ( I I I ) AH
The reaction is preferably carried out in an aprotic solvent, e.g. ether. The temperature can be between -78 and 140C, preferably from 0 to 40C. The compound of the formula II and the compound of the formula III are preferably used in equimolar amounts. The compound of the formula III can also be used in excess, since unreacted metal amide of the formula III can easily be removed by sublimation.
The methods of preparing compounds of the formula II are known (Chem. Ber. 1990, 123, 1649). The methods of preparing compounds of the formula III are likewise known (J. Chem. Soc. A, (1971), 2741).
Organometallic compounds of the formula I are, in combination with a cocatalyst, suitable catalysts for the polymerization of olefins for preparing olefin polymers.
The present invention thus also provides a process for preparing a polyolefin by polymerization of at least one olefin in the presence of a catalyst, wherein the catalyst comprises at least one organometallic compound of the formula I and at least one cocatalyst. The polymerization can be a homopolymerization or a copolymerization.
Preference is given to homopolymerizing or copolymerizing olefins of the formula Ra-CH=CH-Rb, where Ra and Rb are identical or different and are each a hydrogen atom or a hydrocarbon radical having from 1 to 20 carbon atoms, in particular from 1 to 10 carbon atoms, or Ra and Rb together with the atoms connecting them form one or more rings. Examples of such olefins are 1-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene or 1,4-h~YA~iene and cyclic olefins such as norbornene, tetracyclododecene, norbornadiene or vinylnorbornene. In the process of the invention, preference is given to homopolymerizing ethylene or propylene, or copolymerizing ethylene with one or more 1-olefins having 3-20 carbon atoms, for example propylene, and/or one or more dienes having 4-20 carbon atoms, for example 1,4-butadiene. Examples of such copolymers are ethylene-propylene copolymers and ethylene-propylene-1,4-hexadiene copolymers.
The polymerization is preferably carried out at a temperature of from -60 to 250C, particularly preferably from 50 to 200C. The pressure is preferably from 0.5 to 2000 bar, particularly preferably from 5 to 64 bar.
The polymerization can be carried out in ~olution, in bulk, in suspension or in the gas phase, continuously or 21759~;8 batchwise, and in one or more stages. A preferred embodiment is gas-phase polymerization.
The catalyst used in the process of the invention preferably comprises one organometallic compound of the formula I. It is also possible to use mixtures of two or more organometallic compounds of the formula I, or mixtures of organometallic compounds of the formula I
with other metallocenes, semi-sandwich compounds or classic Ziegler-Natta catalysts, e.g. for preparing polyolefins having a broad or multimodal molecular weight distribution.
In principle, a suitable cocatalyst in the process of the invention is any compound which, owing to its ~ewis acidity, can convert the neutral metallocene into a cation and stabilize the latter ("labile coordination").
Furthermore, the cocatalyst or the anion formed therefrom should undergo no further reactions with the metallocene cation formed (EP 427 697). As cocatalyst, preference is given to using an aluminium compound and/or a boron compound.
The boron compound preferably has the formula R5XNH4 XBR64, R5XPH4 xBR64, R53CBR64 or BR63, where x is a number from 1 to 4, preferably 3, the radicals R5 are identical or different, preferably identical, and are C1-C1O-alkyl or C6-C18-aryl, or two radicals R5 together with the atoms connecting them form a ring, and the radicals R6 are identical or different, preferably identical, and are C6-Cl8-aryl which can be substituted by alkyl, haloalkyl or fluorine. In particular, R5 is ethyl, propyl, butyl or phenyl and R6 is phenyl, pentafluorophenyl, 3,5-bistri-fluoromethylphenyl, mesityl, xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).
The cocatalyst used is preferably an aluminium compound such as all ;nox~ne and/or an aluminium alkyl.
~17~968 The cocatalyst used i8 particularly preferably an aluminoxane, in particular of the formula IIa for the linear type and/or the formula IIb for the cyclic type, R~ R4 R~
/ A I--O--A I ~ A I \ ( I V a ) R4 _ _p R~
A I O-- ( I Vb) -- p+2 where, in the formulae IVa and IVb, the radicals R4 are identical or different and are each hydrogen or a C1-C20-hydrocarbon group such as a C1-Cl8-alkyl group, a C6-Cl8-aryl group or benzyl, and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R4 are preferably identical and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals R4 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably being present in a proportion of from 0.01 to 40 % (of the radicals R4).
Methods of preparing the aluminoxanes are known (DE 4 004 477).
The exact spatial structure of the al~m;no~nes iæ not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings are joined to g form larger two-~;mensional or three-dimensional structures.
Regardless of the method of preparation, all alum;noYAne solutions have in common a varying content of unreacted aluminium starting compound, which i8 present in free form or as adduct.
It is possible to preactivate the organometallic compound of the invention prior to use in the polymerization reaction by means of a cocatalyst, in particular an aluminoxane. This significantly increases the polymerization activity. The preactivation of the organometallic compound is preferably carried out in solution. For this purpose, the organometallic compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Preference is given to using toluene.
The concentration of the alum;~oYAne in the solution is in the range from about 1 % by weight to the saturation limit, preferably from 5 to 30 % by weight, in each case based on the total amount of solution. The metallocene can be used in the same concentration, but i8 preferably used in an amount of 10-4-1 mol per mol of aluminoxane.
The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The preactivation is carried out at a temperature of from -78 to 100C, preferably from 0 to 70C.
Here, the organometallic compound is preferably used in a concentration, based on the transition metal, of from 10-3 to 10- mol, preferably from 10-4 to 10-7 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. The alum;no~Ane is preferably used in a concentration of from 10-6 to 10~1 mol, preferably from 10-5 to 10 -2 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the organometallic compound. However, higher concentrations are also possible in principle.
To remove catalyst poisons present in the olefin, purification using an aluminium compound, preferably an aluminium alkyl such as trimethylaluminium or triethylaluminium, is advantageous. This purification can be carried out either in the polymerization system itself, or the olefin is, prior to addition to the polymerization system, brought into contact with the aluminium compound and subsequently separated off again.
As molecular weight regulator and/or for increasing the activity, it is possible to add hydrogen in the process of the invention. This enables low molecular weight polyolefins such as waxes to be obtained.
In the process of the invention, the organometallic compound is preferably reacted with the cocata yst outside the polymerization reactor in a separate step using a suitable solvent. Application to a support can be carried out during this step.
A prepolymerization can be carried out in the process of the invention by means of the organometallic compound.
For the prepolymerization, preference is given to using the (or one of the) olefin(s) used in the polymerization.
The catalyst used in the process of the invention can be supported. The application to a support allows, for example, the particle morphology of the polyolefin prepared to be controlled. Here, the organometallic compound can be reacted first with the support and subsequently with the cocatalyst. However, the cocatalyst can also first be supported and subsequently reacted with the organometallic compound. It is also possible to support the reaction product of organometallic compound and cocatalyst. Suitable support materials are, for ~175968 example, silica gels, aluminium oxides, sol d alum;noxAne or other inorganic support materials such as magnesium chloride. Another suitable support material is a polyolefin powder in finely divided form. The preparation of the supported cocatalyst can be carried out, for example, as described in EP 567 952.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent customary for the Ziegler low-pressure process is used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples which may be mentioned are propane, butane, hexane, heptane, isooctane, cyclohexane, methylcycloheYAne. A petroleum or hydrogenated diesel oil fraction can also be used. It is also possible to use toluene. The polymerization is preferably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in in gaseous or liquid form.
The polymerization time can be any desired, since the catalyst system to be used in the process of the invention has only a slight time-dependent decrease in the polymerization activity.
The polymers prepared by the process of the invention are suitable, in particular, for producing shaped bodies such as films, plates or large hollow bodies (e.g. pipes).
The examples below illustrate the invention:
All glass apparatus was baked out in vacuo and flushed with argon. All operations were carried out with exclusion of moisture and oxygen in Schlenk vessels. The solvents used were distilled under argon from an Na/K
~lloy.
1. Bis(dimethylamido){[(phenylamido)dimethyl-~17~968 silyl]cyclopentadienyl}molybdenum 1:
Mo(N(cH3)2)4 (200 mg, 0.74 mmol) i8 dissolved in 10 ml of Et20 and the violet solution is cooled to -78C.
Dimethyl(cyclopentadienyl)(aminophenyl)silane (158 mg, 0.74 mmol) dissolved in 15 ml of Et20 is slowly added.
The reaction mixture is slowly warmed to room temperature and is stirred overnight at this temperature. The dark red solution is heated under reflux for 2 hours, subsequently filtered and the solvent is removed under reduced pressure. Pentane (about 1 ml) is added and the solution is recrystallized at -78C. 160 mg (60 % yield) of a brown solid are isolated.
lH-NMR (400 MHz, C6D6, 25C, TMS): ~ = 0.25 (8, 6H;
Si(CH3)2), 3.20 (8, 12H; N(CH3)2), 4.88 (t, 2H, 3J(H,H) =
2.1 Hz, C5H4), 6.04 (t, 2H, 3J(H,H) = 2.1 Hz, C5H4), 6.84 (t, lH, 3J(H,H) = 7.1 Hz, para-c6H5)~ 7.07 (d, 2H, 3J(H,H) = 8.6 Hz, ortho-C6H5), 7.23 (t, 2H, 3J(H,H) = 8.0 Hz, meta-C6H5).
2. Bis(dimethylamido){[(tert-butylamido)dimethyl-silyl]indenyl}molybdenum 2:
The preparation is carried out by a method similar to Example 1.
lH-NMR (400 MHz, C6D6, 25C, TMS): ~ = 0.28 (8, 6H;
Si(CH3)2), 1.14 (8, 9H; C(CH3)3), 3.26 (8, 12H; N(CH3)2), 4,79 (d, lH, 3J(H,H) = 2.5 Hz, CgH6)~ 6.06 (d, lH, 3J(H,H) = 2.5 Hz, CgH6)~ 6.87 (t, lH, 3J(H,H) = 7.0 Hz, CgH6)~
6.95 (t, lH, 3J(H,H) = 7.2 Hz, CgH6)~ 7.27 (d, lH, 3J(H,H) = 7.9 Hz, C9H6), 7.65 (d, lH, 3J(H,H) = 7.9 Hz, CgH6)~
3. Bis(dimethylamido)[(cylopentadienyl)(fluorenyl)-isopropylidene]molybdenum 2:
The preparation is carried out by a method similar to Example 1.
~175968 lH-NMR (400 MHz, C6D6, 25C, TMS): ~ = 0.58 (s, 6H;
C(CH3)2), 2.95 (8, 12H; N(CH3)3), 5.21 (t, 2H; 3J(H,H) =
2.4 Hz, C5H4), 5.59 (t, 2H, 3J(H,H) = 2.4 Hz, C5H4), 7.21 (t, 2H, 3J(H,H) = 6.9 Hz, C13H8), 7.49 (d, 2H, 3J(H,H) =
6.7 Hz, C13H8), 7.60 (d, lH, 3J(H,H) -- 6.8 Hz, C13H8), 7.65 (d, 2H, 3J(H,H) = 7.0 Hz, C13H8); MS (CI): m/e (%) =
456.3 (100) [M~].
The preparation is carried out by a method similar to Example 1.
~175968 lH-NMR (400 MHz, C6D6, 25C, TMS): ~ = 0.58 (s, 6H;
C(CH3)2), 2.95 (8, 12H; N(CH3)3), 5.21 (t, 2H; 3J(H,H) =
2.4 Hz, C5H4), 5.59 (t, 2H, 3J(H,H) = 2.4 Hz, C5H4), 7.21 (t, 2H, 3J(H,H) = 6.9 Hz, C13H8), 7.49 (d, 2H, 3J(H,H) =
6.7 Hz, C13H8), 7.60 (d, lH, 3J(H,H) -- 6.8 Hz, C13H8), 7.65 (d, 2H, 3J(H,H) = 7.0 Hz, C13H8); MS (CI): m/e (%) =
456.3 (100) [M~].
Claims (9)
1. An organometallic compound of the formula I
(I) where M is chromium, molybdenum or tungsten, L is a .pi. ligand, T is a bridge, A is a .pi. ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen.
(I) where M is chromium, molybdenum or tungsten, L is a .pi. ligand, T is a bridge, A is a .pi. ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen.
2. An organometallic compound as claimed in claim 1, where L is a substituted or unsubstituted cyclopentadienyl group.
3. An organometallic compound as claimed in claim 1 or 2, where A is a substituted or unsubstituted cyclopentadienyl group.
4. An organometallic compound as claimed in one or more of claims 1 to 3, where T is a bridge [R22B]n, where B is carbon, silicon or germanium and the radicals R2 are identical or different and are each hydrogen or a C1-C30-hydrocarbon radical.
5. A catalyst component comprising at least one organometallic compound as claimed in one or more of claims 1 to 4 and at least one cocatalyst.
6. A catalyst component as claimed in claim 5, additionally containing a support.
7. A process for preparing an organometallic compound of the formula I, ( I ) where M is chromium, molybdenum or tungsten, L is a ligand, T is a bridge, A is a .pi. ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen, which comprises reacting a compound of the formula II
( I I ) where L is a .pi. ligand, T is a bridge and A is a ligand or another electron donor, with a compound of the formula III
M(NR12)4 (III), where M is a tetravalent metal and R1 is a C1-C20-hydrocarbon radical.
( I I ) where L is a .pi. ligand, T is a bridge and A is a ligand or another electron donor, with a compound of the formula III
M(NR12)4 (III), where M is a tetravalent metal and R1 is a C1-C20-hydrocarbon radical.
8. A process for preparing a polyolefin by polymerization of at least one olefin in the presence of a catalyst, wherein the catalyst comprises at least one organometallic compound of the formula I
( I ) where M is chromium, molybdenum or tungsten, L is a ? ligand, T is a bridge, A is a ? ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen, and at least one cocatalyst.
( I ) where M is chromium, molybdenum or tungsten, L is a ? ligand, T is a bridge, A is a ? ligand or another electron donor and R1 are, independently of one another, identical or different C1-C20-hydrocarbon radicals or hydrogen, and at least one cocatalyst.
9. Use of an organometallic compound as claimed in one or more of claims 1 to 4 for olefin polymerization.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19516801.1 | 1995-05-08 | ||
| DE19516801A DE19516801A1 (en) | 1995-05-08 | 1995-05-08 | Organometallic compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2175968A1 true CA2175968A1 (en) | 1996-11-09 |
Family
ID=7761336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002175968A Abandoned CA2175968A1 (en) | 1995-05-08 | 1996-05-07 | Organometallic compound |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5808122A (en) |
| EP (1) | EP0742046B1 (en) |
| JP (1) | JP3751361B2 (en) |
| KR (1) | KR960041199A (en) |
| AT (1) | ATE203429T1 (en) |
| BR (1) | BR9602180A (en) |
| CA (1) | CA2175968A1 (en) |
| DE (2) | DE19516801A1 (en) |
| ES (1) | ES2161314T3 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19522013A1 (en) * | 1995-06-21 | 1997-01-02 | Hoechst Ag | Transition metal compound |
| US6169152B1 (en) * | 1996-07-05 | 2001-01-02 | Jsr Corporation | Olefin polymerization catalyst comprising transition metal compound containing a cyclic ligand having at least two nitrogen atoms in its main chain skeleton |
| DE19710615A1 (en) * | 1997-03-14 | 1998-09-17 | Studiengesellschaft Kohle Mbh | New catalysts for polymerisation of alkene |
| JP3566819B2 (en) * | 1996-10-04 | 2004-09-15 | 関東化学株式会社 | New organic transition metal compounds |
| DE19728126A1 (en) * | 1997-07-02 | 1999-01-07 | Bayer Ag | Catalyst system based on monoazadiene metal complexes |
| EP0933383A1 (en) | 1998-01-29 | 1999-08-04 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for the polymerization of olefins |
| EP1010709A1 (en) | 1998-12-14 | 2000-06-21 | Fina Research S.A. | Metallocene compound and its use for polyolefin production |
| US6437161B1 (en) * | 1999-08-13 | 2002-08-20 | Basf Aktiengesellschaft | Monocyclopentadienyl complexes of chromium, molybdenum or tungsten |
| JP4766782B2 (en) * | 2001-06-20 | 2011-09-07 | 株式会社半導体エネルギー研究所 | ORGANIC LIGHT EMITTING ELEMENT, AND LIGHT EMITTING DEVICE, ELECTRIC APPLIANCE, AND LIGHTING DEVICE USING THE SAME |
| US20060089253A1 (en) * | 2002-08-13 | 2006-04-27 | Shahram Mihan | Monocyclopentadienyl complexes |
| DE60314262T2 (en) | 2002-08-22 | 2008-01-31 | Basell Polyolefine Gmbh | monocyclopentadienyl |
| EP1572360B1 (en) | 2002-12-20 | 2008-06-25 | Basell Polyolefine GmbH | Monocyclopentadienyl complexes |
| MXPA05006583A (en) | 2002-12-20 | 2005-12-14 | Basell Polyolefine Gmbh | COPOLYMERS OF ETHYLENE WITH alpha-OLEFINS. |
| US7544826B2 (en) | 2003-12-16 | 2009-06-09 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
| WO2005058983A2 (en) | 2003-12-19 | 2005-06-30 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
| DE102004061618A1 (en) * | 2004-12-17 | 2006-06-22 | Basell Polyolefine Gmbh | New monocyclopentadienyl complex useful as catalyst for polymerization of olefin comprises cyclopentadienyl system containing bridged donor and arylalkyl group at the cyclopentadienyl system |
| EP3274378A4 (en) * | 2015-03-23 | 2018-12-12 | ExxonMobil Chemical Patents Inc. | Group 6 transition metal catalyst compound and use thereof |
| US10329363B2 (en) | 2015-03-23 | 2019-06-25 | Exxonmobil Chemical Patents Inc. | Group 6 transition metal catalyst compound and use thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE177759T1 (en) * | 1986-09-24 | 1999-04-15 | Mitsui Chemicals Inc | METHOD FOR OLEFIN POLYMERIZATION |
| US4892851A (en) * | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
| DE3942363A1 (en) * | 1989-12-21 | 1991-06-27 | Hoechst Ag | METHOD FOR PRODUCING A POLYPROPYLENE MOLDING MATERIAL |
| US5272236A (en) * | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
| US5391789A (en) * | 1991-08-08 | 1995-02-21 | Hoechst Aktiengesellschaft | Bridged, chiral metallocenes, processes for their preparation and their use as catalysts |
| TW300901B (en) * | 1991-08-26 | 1997-03-21 | Hoechst Ag | |
| US5278272A (en) * | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
| US5434116A (en) * | 1992-06-05 | 1995-07-18 | Tosoh Corporation | Organic transition metal compound having π-bonding heterocyclic ligand and method of polymerizing olefin by using the same |
| TW294669B (en) * | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
| IT1256603B (en) * | 1992-10-30 | 1995-12-12 | Enichem Polimeri | CATALYST AND PROCEDURE FOR (CO) POLYMERIZING ALPHA-OLEFINS |
| US5320996A (en) * | 1992-11-06 | 1994-06-14 | Chevron Research And Technology Company | Alpha-olefin polymerization catalysts comprising supported cyclopentadienyl group 6b metal oxo, thio, imido and phosphido compounds and process for polymerizing alpha-olefins |
| EP0598543B1 (en) * | 1992-11-10 | 1997-01-15 | Mitsubishi Chemical Corporation | Method for producing Alpha-olefin polymers |
| DE4330667A1 (en) * | 1993-09-10 | 1995-03-16 | Basf Ag | Process for the preparation of multiphase homo- or copolymers of C¶2¶-C¶1¶¶0¶-Alk-1-enes in one reaction zone |
| US5597935A (en) * | 1994-06-01 | 1997-01-28 | University Of Iowa Research Foundation | Synthesis of ansa-metallocene catalysts |
-
1995
- 1995-05-08 DE DE19516801A patent/DE19516801A1/en not_active Withdrawn
-
1996
- 1996-04-30 EP EP96106794A patent/EP0742046B1/en not_active Expired - Lifetime
- 1996-04-30 DE DE59607344T patent/DE59607344D1/en not_active Expired - Fee Related
- 1996-04-30 AT AT96106794T patent/ATE203429T1/en not_active IP Right Cessation
- 1996-04-30 ES ES96106794T patent/ES2161314T3/en not_active Expired - Lifetime
- 1996-05-07 CA CA002175968A patent/CA2175968A1/en not_active Abandoned
- 1996-05-07 BR BR9602180A patent/BR9602180A/en active Search and Examination
- 1996-05-07 KR KR1019960014756A patent/KR960041199A/en not_active Application Discontinuation
- 1996-05-08 JP JP11367696A patent/JP3751361B2/en not_active Expired - Fee Related
- 1996-05-08 US US08/646,876 patent/US5808122A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5808122A (en) | 1998-09-15 |
| EP0742046A2 (en) | 1996-11-13 |
| JPH08301890A (en) | 1996-11-19 |
| ATE203429T1 (en) | 2001-08-15 |
| EP0742046A3 (en) | 1997-06-11 |
| EP0742046B1 (en) | 2001-07-25 |
| BR9602180A (en) | 1998-04-07 |
| KR960041199A (en) | 1996-12-19 |
| DE19516801A1 (en) | 1996-11-14 |
| ES2161314T3 (en) | 2001-12-01 |
| DE59607344D1 (en) | 2001-08-30 |
| JP3751361B2 (en) | 2006-03-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |