CA2200243A1 - Method for producing highly active, stable metallocene catalyst systems,and formulations produced thereby - Google Patents
Method for producing highly active, stable metallocene catalyst systems,and formulations produced therebyInfo
- Publication number
- CA2200243A1 CA2200243A1 CA002200243A CA2200243A CA2200243A1 CA 2200243 A1 CA2200243 A1 CA 2200243A1 CA 002200243 A CA002200243 A CA 002200243A CA 2200243 A CA2200243 A CA 2200243A CA 2200243 A1 CA2200243 A1 CA 2200243A1
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- Prior art keywords
- bis
- zirconium dichloride
- dichloride
- cocatalyst
- indenyl
- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed are a method for the production of homogeneous, highly active, stable formulations, consisting essentially of one or more organometallic catalyst components in paraffins, and formulations produced according to this method.
Description
~2ûJ243 ME:THOD F~R PRÇ)L)UC lNl; HIGHLY ACTIVE, STABLE METALLOCENE
C~TALYST SYSTEMS, AND FORMULATIONS PROL~U~ H~ Ry Backqround of the Invention Metallocene catalyst systems are increasingly gaining in importance as a new generation of catalyst systems for the production of polyolefins ("Single Site Catalysts"). As is already known from classical Ziegler-Natta catalysis, these new catalysts essentially consist of a transition-metal compound as a catalyst and a cocatalyst component, for example, an alkylaluminoxane, in particular, methylaluminoxane.
Cyclopentadienyl, indenyl, or fluorenyl derivatives of group IVA of the Periodic Table of the Elements are preferably used as the transition metal compound. In contrast to conventional Ziegler-Natta catalysts, such systems have, in addition to a high activity and productivity, not only the capability of a specific control of product characteristics as a function of the components used and the reaction conditions, but, moveover, they open up access to previously unknown polymer structures with very promising characteristics with regard to technical applications.
In the literature, a large number of publications have appeared having as an object the production of special polyolefins with such catalyst systems. What is disadvantageous in almost all cases, however, is the fact that to attain acceptable productivities, a high excess of alkylaluminoxanes, based on-the transition metal component, is required (usually, the ratio of aluminum, in the form of 2~0~243 1 aluminoxane, to transition metal is approximately 1000:1). Due to the high price of the alkylaluminoxanes, on the one hand, and due to the additional polymer work-up steps ("dea~hing stepsn), required in some cases, on the other hand, a polymer production on a technical scale and on the basis of such catalyst systems would frequently be uneconomical. In addition, there is the fact that the solvent toluene, frequently used for the formulation of alkylaluminoxanes, in particular, methylaluminoxane, is increasingly undesired for reasons of the storage stability of highly concentrated formulations (strong tendency to gel formation of the alllm;noxane solutions) and for toxicological reasons, with respect to the application range of the polyolefins that result in the long run.
These catalyst systems or their formulations are very sensitive subs~ances that undergo losses in polymerization activity within a few hours or days.
Due to the high price of these modern catalyst systems, such activity losses are not acceptable. For economic reasons, therefore, there has been a need for catalysts or catalyst systems - which, after production, remain highly active for a longer period of time or even increase in acti~ity.
According to World Patent No. 93/23439, the stability of metallocene catalyst systems is attained by a comprehensive variation of the preparation conditions, in particular, temperature treatment.
3o 22~)2~3 1 This procedure is expensive, on the one hand, and cannot generally be used because of the sensitivity of the systems, on the other hand.
The goal of the present invention, therefore, is to overcome these disadvantages and to develop homogeneous formulations of metallocene-based catalyst systems that at least retain their high polymerization activity over a long period of time.
Brief SummarY of the Invention Surprisingly, it has been discovered that the polymerization activity of metallocene catalyst systems in the form of paraffin-containing, liquid or solid formulations can be stabilized permanently. The definition formulation, therefore, comprises catalyst systems in high-boiling hydrocarbons (paraffins) of a consistency which is oily or waxy at room temperature, in which the components are dissolved, suspended, or dispersed by means of suitable mixing devices.
An object of the invention is therefore a method for the production of homogeneous mixtures, consisting essentially of at least one metallocene, at least one cocatalyst, and a formulation medium, wherein the preparation of the catalyst component, A) takes place directly in the formulation medium according to methods which are, in fact, known;
- or B) the metallocene-based catalyst components are prepared and isolated separately and then 22u~3243 1 suspended, dispersed, or dissolved in the formulation medium; or C) a solution of the metallocene-based catalyst component, produced according to known methods, in a low-boiling solvent, is introduced, in a first step, into the formulation medium, and in a second step, the l.ow-boiling solvent is removed, D) optionally in the presence of any of the customary inorganic or organic carrier materials, auxiliaries, additives, and/or accessory agents.
Another object of the invention refers to the formulations produced in accordance with the method of the invention.
Other objects of the invention are characterized by the claims.
Detailed Description of the Invention The formulation media useful according to this invention include all natural or synthetic, commercially available long-chain, optionally branched, liquid or solid hydrocarbons with boiling points above 150~C, preferably above 200~C, and viscosities of at least 1 Pa-sec at 25~C.
These compounds include the product groups of the so-called white mineral oils, e.g. Witco White Mineral Oil Parol~ (trademark of Witco Polymers ~
Resins B.V., Netherlands), petrolatum (Vaseline), and paraffinic waxes, e.g., Terhell~ (Schumann Company).
2~0U24~
1 The hydrocarbon used does not depend on the organometallic compound but is determined mainly by practical requirements of future applications.
Compounds of the elements of Groups IIA, 5 IIIA, or IVA of the Periodic Table of the Elements, preferably organoaluminum, organoboron, or organomagnesium substances, alone or in mixtures, or as a complex salt, are used as cocatalysts, in accordance with the invention, such as RlR2R3Al, RlR2R3B, and R1R2Mg, wherein Rl, R2, R3 are independently of one another halogen, a heteroatom, or alkyl or alkoxy containing up to 12 carbon atoms, for example:
tributylaluminum, triisobutylaluminum, trihexylalllminl~m, trioctylaluminum, diethylaluminum ]5 chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, diethylaluminum iodide, diisobutyl hydride, diethylaluminum methoxide, isoprenylaluminum, dimethylaluminum chloride, methylalulllinoxane, methylaluminum sesquichloride, tetraisobutyl dialuminoxane, trimethyl aluminum, and/or triethylaluminum, preferably in mixtures with at least one of the compounds diethylaluminum hydride, hexaisobutyltetraluminoxane, diethyl (dimethylethylsilanolato)aluminum, diethyl(ethylmesthylsilanolato)aluminum, diisobutyl(methylsilanolato)aluminum, tridodecylaluminum, tripropylaluminum, dipropylaluminum chloride, dibutylmagnesium, butylethylmagnesium, butyloctylmagnesium, 22 ù~243 1 butyloctylmagnesium ethoxide, ethylalllminl-m propoxychloride, triethylboron, tris(pentafluorophenyl)borane, and their salts.
As a catalyst component, one can metallocene compounds as described in European Patent Nos.
A-0,480,390, A-0,413,326, A-0,530,908, A-0,344,887, A-0,420,436, A-0,416,815, A-0,520,732.
They are, in particular compounds of the following general formula QtcpRa)(cp~R~a)M(x)n (1) whereln Cp is a cyclopentadienyl, indenyl or fluorenyl radical;
R and R' are the same or different and each is a Cl-C10 alkyl, phosphine, amine, Cl-C10 alkyl ether, or C6-ClO
aryl ether group with O<a~4 and O<a'<4;
Cp' is one of the groups Cp or Cp~ is -NR~- wherein-R~ is an alkyl or aryl radical and a=1, and Q is a single bridge or multi bridges (Rl-Z-R2) b between Cp and Cp', wherein Rl and R2 are the same or different and each is a hydrogen atom, Cl-C10 alkyl group, or C6-C10 aryl group, and Z denotes carbon, 3~ silicon, or germanium, wherein b is 0, 1, 2, or 3, 22~iU24~
1 M is a transition metal of the groups 3 to 6 of the Periodic Table of the Elements ~IUPAC notation), in particular Zr or Hf, X is halogen, in particular, Cl or Br, and n is the oxidation number of M, reduced by 2.
In particular, the following compounds can be used as bridged ligands, Q(CpRa)(Cp'R'a) in general formula (1):
Dimethylsilylbis(1-indene), dimethylsilylbis(l-cyclopentadiene), 2,2-propylbis(1-indene), 2,2-propylbis(trismethylcyclopentadiene), 2,2-propylbis(5-dimethylamino-1-indene), 2,2-propylbis(6-dipropylamino-1-indene), 2,2-propylbis(4,7-bis(dimethylamino-1-indene)), 2,2-propylbis(5-diphenylphosphino-1-indene), 2,2-propylbis(4,5,6,7-tetrahydro-1-indene), 2,2-propylbis(4-methyl-1-indene), 2,2-propylbis(5-methyl-1-indene), 2,2-propylbis(6-methyl-1-indene),2,2-propylbis(7-methyl-l-indene), 2,2-propyl-bis(5-methoxy-1-indene), 2,2-propylbis(4,7-dimethoxy-1-indene), 2,2-propylbis(2,3-dimethyl-1-indene), - 25 2,2-propylbis(4,7-dimethyl-1-indene), 2,2-propylbi~(1-cyclopentadiene), 2,2-propylbis(1-indene), diphenylmethylbis(1-indene), diphenylmethylbis(l-cyclopentadiene), - -diphenylmethylbis(l-indene), 3o 22i:)(i24~
1 diphenylsilylbis(l-indene)r diphenylsilylbis(1-cyclopentadiene), diphenylsilylbis(l-indene), ethylenebis(1-indene), ethylenebis(trimethylcyclopentadiene), ethylenebis(5-dimethylamino-1-indene), ethylenebis(6-dipropylamino-1-indene), ethylenebis(4,7-bisdimethylamino-1-indene), ethylenebis(5-diphenylphosphino-1-indene), ethylenebis(4,5,6,7-tetrahydro-1-indene), ethylenebis(6-methyl-1-indene), ethylenebis(7-methyl-1-indene), ethylenebis(5-methoxy-1-indene), ethylenebis(4,7-dimethoxy-1-indene), ethylenebis(2,3-dimethyl-1-indene), ethylenebis(4,7-dimethyl-1-indene), ethylenebis(9-fluorene), ethylenebis(1-cyclopentadiene), ethylenebis(1-indene).
As unbridged ligands (formula (1) with b =
0), preferably the following compounds can be used:
cyclopentadiene, fluorene, indene, and their monoalkylated or multialkylated derivatives, wherein - the alkyl radical can contain 1-10 ca~bon atoms. In accordance with the invention, the following are pre-ferred:
[bis(cyclopentadienyl)]zirconium dichloride, [bis(methylcyclopentadienyl)~zirconium dichloride, [bis(n-propylcyclopentadienyl)]zirconium dichloride, [bis(isobutylcyclopentadienyl)]zirconium dichloride, [bis(cyclopentylcyclopentadienyl)~zirconium dichloride, ~2 ù~i243 1 [bis(benzylcyclopentadienyl)]zirconium dichloride, [bis(octadecylcyclopentadienyl)3zirconium dichloride, [bis(n-butylcyclopentadienyl)]titanium dichloride, [bis(n-butylcyclopentadienyl)~zirconium dichloride, [bis(n-butylcyclopentadienyl)]hafnium dichloride, ~bis(indenyl)]zirconium dichloride, [bis(indenyl)]dimethylzirconium, [bis(tetrahydroindenyl)]zirconium dichloride, [1,2-ethylenebis(indenyl)]zirconium dichloride, [1,2-ethylenebis(indenyl)hafnium dichloride, [1,2-ethylenebis(tetrahydroindenyl)zirconium dichloride, [dimethylsilylbis(lH-inden-1-yl]zirconium dichloride, [dimethylsilylbis(lH-inden-l-yl)]hafnium dichloride.
Porous oxides of one or more of the elements of groups IIA, IIIA, or IVA of the Periodic Table of the Elements, such as ZrO2, Tio2, B203, CaO, ZnO, BaO, preferably aluminosilicates (zeolites), Al203 and MgO
and in particular, SiO2 (West German Patent No.
C~TALYST SYSTEMS, AND FORMULATIONS PROL~U~ H~ Ry Backqround of the Invention Metallocene catalyst systems are increasingly gaining in importance as a new generation of catalyst systems for the production of polyolefins ("Single Site Catalysts"). As is already known from classical Ziegler-Natta catalysis, these new catalysts essentially consist of a transition-metal compound as a catalyst and a cocatalyst component, for example, an alkylaluminoxane, in particular, methylaluminoxane.
Cyclopentadienyl, indenyl, or fluorenyl derivatives of group IVA of the Periodic Table of the Elements are preferably used as the transition metal compound. In contrast to conventional Ziegler-Natta catalysts, such systems have, in addition to a high activity and productivity, not only the capability of a specific control of product characteristics as a function of the components used and the reaction conditions, but, moveover, they open up access to previously unknown polymer structures with very promising characteristics with regard to technical applications.
In the literature, a large number of publications have appeared having as an object the production of special polyolefins with such catalyst systems. What is disadvantageous in almost all cases, however, is the fact that to attain acceptable productivities, a high excess of alkylaluminoxanes, based on-the transition metal component, is required (usually, the ratio of aluminum, in the form of 2~0~243 1 aluminoxane, to transition metal is approximately 1000:1). Due to the high price of the alkylaluminoxanes, on the one hand, and due to the additional polymer work-up steps ("dea~hing stepsn), required in some cases, on the other hand, a polymer production on a technical scale and on the basis of such catalyst systems would frequently be uneconomical. In addition, there is the fact that the solvent toluene, frequently used for the formulation of alkylaluminoxanes, in particular, methylaluminoxane, is increasingly undesired for reasons of the storage stability of highly concentrated formulations (strong tendency to gel formation of the alllm;noxane solutions) and for toxicological reasons, with respect to the application range of the polyolefins that result in the long run.
These catalyst systems or their formulations are very sensitive subs~ances that undergo losses in polymerization activity within a few hours or days.
Due to the high price of these modern catalyst systems, such activity losses are not acceptable. For economic reasons, therefore, there has been a need for catalysts or catalyst systems - which, after production, remain highly active for a longer period of time or even increase in acti~ity.
According to World Patent No. 93/23439, the stability of metallocene catalyst systems is attained by a comprehensive variation of the preparation conditions, in particular, temperature treatment.
3o 22~)2~3 1 This procedure is expensive, on the one hand, and cannot generally be used because of the sensitivity of the systems, on the other hand.
The goal of the present invention, therefore, is to overcome these disadvantages and to develop homogeneous formulations of metallocene-based catalyst systems that at least retain their high polymerization activity over a long period of time.
Brief SummarY of the Invention Surprisingly, it has been discovered that the polymerization activity of metallocene catalyst systems in the form of paraffin-containing, liquid or solid formulations can be stabilized permanently. The definition formulation, therefore, comprises catalyst systems in high-boiling hydrocarbons (paraffins) of a consistency which is oily or waxy at room temperature, in which the components are dissolved, suspended, or dispersed by means of suitable mixing devices.
An object of the invention is therefore a method for the production of homogeneous mixtures, consisting essentially of at least one metallocene, at least one cocatalyst, and a formulation medium, wherein the preparation of the catalyst component, A) takes place directly in the formulation medium according to methods which are, in fact, known;
- or B) the metallocene-based catalyst components are prepared and isolated separately and then 22u~3243 1 suspended, dispersed, or dissolved in the formulation medium; or C) a solution of the metallocene-based catalyst component, produced according to known methods, in a low-boiling solvent, is introduced, in a first step, into the formulation medium, and in a second step, the l.ow-boiling solvent is removed, D) optionally in the presence of any of the customary inorganic or organic carrier materials, auxiliaries, additives, and/or accessory agents.
Another object of the invention refers to the formulations produced in accordance with the method of the invention.
Other objects of the invention are characterized by the claims.
Detailed Description of the Invention The formulation media useful according to this invention include all natural or synthetic, commercially available long-chain, optionally branched, liquid or solid hydrocarbons with boiling points above 150~C, preferably above 200~C, and viscosities of at least 1 Pa-sec at 25~C.
These compounds include the product groups of the so-called white mineral oils, e.g. Witco White Mineral Oil Parol~ (trademark of Witco Polymers ~
Resins B.V., Netherlands), petrolatum (Vaseline), and paraffinic waxes, e.g., Terhell~ (Schumann Company).
2~0U24~
1 The hydrocarbon used does not depend on the organometallic compound but is determined mainly by practical requirements of future applications.
Compounds of the elements of Groups IIA, 5 IIIA, or IVA of the Periodic Table of the Elements, preferably organoaluminum, organoboron, or organomagnesium substances, alone or in mixtures, or as a complex salt, are used as cocatalysts, in accordance with the invention, such as RlR2R3Al, RlR2R3B, and R1R2Mg, wherein Rl, R2, R3 are independently of one another halogen, a heteroatom, or alkyl or alkoxy containing up to 12 carbon atoms, for example:
tributylaluminum, triisobutylaluminum, trihexylalllminl~m, trioctylaluminum, diethylaluminum ]5 chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, diethylaluminum iodide, diisobutyl hydride, diethylaluminum methoxide, isoprenylaluminum, dimethylaluminum chloride, methylalulllinoxane, methylaluminum sesquichloride, tetraisobutyl dialuminoxane, trimethyl aluminum, and/or triethylaluminum, preferably in mixtures with at least one of the compounds diethylaluminum hydride, hexaisobutyltetraluminoxane, diethyl (dimethylethylsilanolato)aluminum, diethyl(ethylmesthylsilanolato)aluminum, diisobutyl(methylsilanolato)aluminum, tridodecylaluminum, tripropylaluminum, dipropylaluminum chloride, dibutylmagnesium, butylethylmagnesium, butyloctylmagnesium, 22 ù~243 1 butyloctylmagnesium ethoxide, ethylalllminl-m propoxychloride, triethylboron, tris(pentafluorophenyl)borane, and their salts.
As a catalyst component, one can metallocene compounds as described in European Patent Nos.
A-0,480,390, A-0,413,326, A-0,530,908, A-0,344,887, A-0,420,436, A-0,416,815, A-0,520,732.
They are, in particular compounds of the following general formula QtcpRa)(cp~R~a)M(x)n (1) whereln Cp is a cyclopentadienyl, indenyl or fluorenyl radical;
R and R' are the same or different and each is a Cl-C10 alkyl, phosphine, amine, Cl-C10 alkyl ether, or C6-ClO
aryl ether group with O<a~4 and O<a'<4;
Cp' is one of the groups Cp or Cp~ is -NR~- wherein-R~ is an alkyl or aryl radical and a=1, and Q is a single bridge or multi bridges (Rl-Z-R2) b between Cp and Cp', wherein Rl and R2 are the same or different and each is a hydrogen atom, Cl-C10 alkyl group, or C6-C10 aryl group, and Z denotes carbon, 3~ silicon, or germanium, wherein b is 0, 1, 2, or 3, 22~iU24~
1 M is a transition metal of the groups 3 to 6 of the Periodic Table of the Elements ~IUPAC notation), in particular Zr or Hf, X is halogen, in particular, Cl or Br, and n is the oxidation number of M, reduced by 2.
In particular, the following compounds can be used as bridged ligands, Q(CpRa)(Cp'R'a) in general formula (1):
Dimethylsilylbis(1-indene), dimethylsilylbis(l-cyclopentadiene), 2,2-propylbis(1-indene), 2,2-propylbis(trismethylcyclopentadiene), 2,2-propylbis(5-dimethylamino-1-indene), 2,2-propylbis(6-dipropylamino-1-indene), 2,2-propylbis(4,7-bis(dimethylamino-1-indene)), 2,2-propylbis(5-diphenylphosphino-1-indene), 2,2-propylbis(4,5,6,7-tetrahydro-1-indene), 2,2-propylbis(4-methyl-1-indene), 2,2-propylbis(5-methyl-1-indene), 2,2-propylbis(6-methyl-1-indene),2,2-propylbis(7-methyl-l-indene), 2,2-propyl-bis(5-methoxy-1-indene), 2,2-propylbis(4,7-dimethoxy-1-indene), 2,2-propylbis(2,3-dimethyl-1-indene), - 25 2,2-propylbis(4,7-dimethyl-1-indene), 2,2-propylbi~(1-cyclopentadiene), 2,2-propylbis(1-indene), diphenylmethylbis(1-indene), diphenylmethylbis(l-cyclopentadiene), - -diphenylmethylbis(l-indene), 3o 22i:)(i24~
1 diphenylsilylbis(l-indene)r diphenylsilylbis(1-cyclopentadiene), diphenylsilylbis(l-indene), ethylenebis(1-indene), ethylenebis(trimethylcyclopentadiene), ethylenebis(5-dimethylamino-1-indene), ethylenebis(6-dipropylamino-1-indene), ethylenebis(4,7-bisdimethylamino-1-indene), ethylenebis(5-diphenylphosphino-1-indene), ethylenebis(4,5,6,7-tetrahydro-1-indene), ethylenebis(6-methyl-1-indene), ethylenebis(7-methyl-1-indene), ethylenebis(5-methoxy-1-indene), ethylenebis(4,7-dimethoxy-1-indene), ethylenebis(2,3-dimethyl-1-indene), ethylenebis(4,7-dimethyl-1-indene), ethylenebis(9-fluorene), ethylenebis(1-cyclopentadiene), ethylenebis(1-indene).
As unbridged ligands (formula (1) with b =
0), preferably the following compounds can be used:
cyclopentadiene, fluorene, indene, and their monoalkylated or multialkylated derivatives, wherein - the alkyl radical can contain 1-10 ca~bon atoms. In accordance with the invention, the following are pre-ferred:
[bis(cyclopentadienyl)]zirconium dichloride, [bis(methylcyclopentadienyl)~zirconium dichloride, [bis(n-propylcyclopentadienyl)]zirconium dichloride, [bis(isobutylcyclopentadienyl)]zirconium dichloride, [bis(cyclopentylcyclopentadienyl)~zirconium dichloride, ~2 ù~i243 1 [bis(benzylcyclopentadienyl)]zirconium dichloride, [bis(octadecylcyclopentadienyl)3zirconium dichloride, [bis(n-butylcyclopentadienyl)]titanium dichloride, [bis(n-butylcyclopentadienyl)~zirconium dichloride, [bis(n-butylcyclopentadienyl)]hafnium dichloride, ~bis(indenyl)]zirconium dichloride, [bis(indenyl)]dimethylzirconium, [bis(tetrahydroindenyl)]zirconium dichloride, [1,2-ethylenebis(indenyl)]zirconium dichloride, [1,2-ethylenebis(indenyl)hafnium dichloride, [1,2-ethylenebis(tetrahydroindenyl)zirconium dichloride, [dimethylsilylbis(lH-inden-1-yl]zirconium dichloride, [dimethylsilylbis(lH-inden-l-yl)]hafnium dichloride.
Porous oxides of one or more of the elements of groups IIA, IIIA, or IVA of the Periodic Table of the Elements, such as ZrO2, Tio2, B203, CaO, ZnO, BaO, preferably aluminosilicates (zeolites), Al203 and MgO
and in particular, SiO2 (West German Patent No.
4,409,249), are useful as inorganic carrier materials that can be.used in accordance with the invention.
Porous, partially polymeric compounds, such as polyethylene, polypropylene, polystyrene, and-sugar derivatives (starch, amylose, cyclodextrins), can be taken into consideration as organic carrier materials that can be used in accordance with the invention.
To prepare the formulations of the--invention, in accordance with the method of the invention, there are basically different possibilities, for example:
~20~)243 1 M1) Preparat_on of the metallocene-based catalyst system in the dispersing /suspending medium or solvent (paraffin), in accordance with the lnvention.
M2) Dissolution, suspension, or dispersion of already isolated metallocene-based catalyst components in the dispersing medium or solvent (paraffin), in accordance with the invention M3) Mixing of nonaromatic solvent or dispersing agent with a solution of the metallocene-based catalyst components and subsequent separation of the solvent by means of distillation, thus obtaining the solutions, suspensions, or dispersions, in accordance with the invention.
To prepare the formulations, the catalyst components can be used in pure form as well a~ on a suitable support material. If the catalyst components are used in pure ~orm, the support material and auxiliaries, additives, and accessory agents can be added to the processing possibilities M1)-M3) at any time.
The following examples illustrate the synthesis of the claimed metallocene-catalyst systems and their testing in the polymerization.
22 ~J~2i~3 --ll--1 Synthesis Examples Example 1 Methylaluminoxane in Witco Parol~ (trade name of Witco Netherlands) 402 g of a toluene solution of MA0 (Al total, 13.2%; Al as TMA, 3.19~) and 219 g Witco Parol~
were fed under nitrogen atmosphere to a 1-~ flask, equipped with a thermometer and stirrer that moves around the edges. The flask contents were heated in an oil bath to a m~;ml~m 32~C and a vacuum was applied. The distilled-off toluene was condensed in a low-temperature trap. It was possible to strengthen the vacuum with the declining toluene content of the suspension. Toluene residues were distilled off at cl mbar for 3 h.
A viscous and milky-turbid suspension was obtained. The suspension wa~ neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 13.4%
Al as TMA: 1.5 Example 2 Methylaluminoxane in Witco Petroleum Jelly Snowwhite MD~ (Vaseline, Witco Netherlands) 3o ~ ~ ù~2~3 l 130.1 g of a toluene solution of MA0 (Al total, 13.2; Al as TMA, 3.19%) and 85.1 g White Petroleum Jelly Snowwhite MD~ were fed into a 500-mL
Schlenk tube, equipped with a stirrer, under a protective nitrogen atmosphere. After heating to 55-60~C in an oil bath, the mixture became homogeneous.
The toluene was distilled off in a vacuum and condensed in a low-temperature trap. The vacuum was continuously increased to below 1 mbar, and the bath temperature was maintained at a maximum of 65~C.
After complete ~e-,loval of the toluene, a colorless, homogeneous, waxlike mass was obtained, which flowed at approximately 60~C.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 12.0%
Al as TMA: 1.9%
ExamPle 3 Methylaluminoxane in paraffin wax 33.5 g Methylaluminoxane (solid) and 16.8 g paraffin (Terhell 5605~, Schumann Company) were heated under nitrogen in a round-bottomed flask with a stirrer that moves around the edges. With a bath temperature of 65-70~C, a turbid melt was obtained.
The melt was allowed to solidify while stirring and then the melt was dissolved from the walls of the ~ ' IJ~.i243 .
1 flask. After cooling externally with dry ice, it was possible to comminute the solid to a fine grain solid which could be poured.
The powder, containing approximately 66%
MA0, was not pyrophoric or self-igniting.
Al total: 26.1 Al as TMA: 3.5 Example 4 Methylaluminoxane in Witco Parol~
26.3 g of a finely pulverized MA0 solid (Al total, 39.2%) were stirred with 7.3 g white oil Witco Parol~ under a protective argon atmosphere. A
colorless, waxlike mass was obtained.
The powder containing approximately 78~ MA0 was not pyrophoric or self-igniting and exhibited only a moderate gas development upon contact with water.
Placed on moist filter paper, carbonization without self-ignition was observed.
Al total: 30.1 Al as TMA: 3.6 Example 5 Dispersion of methylaluminoxane in petrolatum (Vaseline) Under a protective nitrogen atmosphere, 125 g of a toluene solution of MA0 (Al total, 13.2~; Al as 2~)2~3 l TMA, 3.19%) and 78.5 g petrolatum, white, German Pharmacopoeia 10, VARH AB (Sch*m~nn Company) were fed into a 500-mL Schlenk tube, equipped with a stirrer.
After heating to 55-60~, the toluene was distilled off and condensed in a low-temperature trap. The vacuum was continuously increased to below 1-mbar, and the bath temperature was maintained at a m~;m1]m 65~C.
After complete le...Jvdl of the toluene, a colorless, homogeneous dispersion was obtained, which could flow at above approximately 60~C.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 12.3 15 Al as TMA: 1.6 Example 6 Suspension of methylaluminoxane and metallocene in 20 white oil - 60.5 g of a toluene solution of MA0 (Al content, 13.2~; Al as TMA, 3.19~) were fed into a stirring apparatus under a protective argon 25 atmosphere. 2.0 g EURECEN~ 5036 (trade name of the Witco Company, Bergkamen, Germany - 1,2-ethylenebis(1-indenyl)zirconium dichloride) were added to this solution, and stirring was carried out for 30 min. 39 g white oil Witco Parol~ were metered into this dark-brown solution and heated to 40~C. The toluene was 2~ 1ulu243 l distilled off under a vacuum of up to 0.1 mbar and condensed in a low-temperature trap.
56.6 g of a brown, waxli~e catalyst mass was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 14.11%
Zr: 0.77%
Example 7 The procedure was carried out as in Example 6. Before use in the polymerization, the mixture was subjected to a 24-h aging process in toluene.
Example 8 The procedure was carried out as in Example 6. Before use in-the polymerization, the mixture was subjected to a 48-h aging process in toluene.
Example 9 Suspension of supported MA0/metallocene/silica catalyst system in Witco Parol~
23 g of a supported catalyst system (TA
02954, research product from the Witco Company; Al 22 i~u2~3 l content, 23.9~, Zr content 1.1~) were stirred with 53.7 g while oil Witco Parol~ in a stirred vessel under a protective argon atmosphere. A dark-brown suspension was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 7.17 Zr total: 0.33 Example 10 Metallocene/methylaluminoxane/silica suspension in white oil 203.5 g of a 10~ solution of methylaluminoxane in toluene (Al content, 5.0~) were introduced into an apparatus suitable for working under a protective argon atmosphere, with stirrer, thermometer, reflux condenser, and metering of solids.
18.8 g Silica (SYLOPOL 2104~, ~race Company, with 5% water content) were thoroughly shaken with 1.5 g distilled water for approximately 10 min, poured into the solids meter, and slowly added to the stirred methylalllm;noxane solution. With gas development (methane gas), the temperature rose to 65~C. After the end of the addition, stirring was carried out - until room temperature was once again reached, and then 2.44 g EURECEN~ 5036 1,2-ethylenebis(1-indenyl)zirconium dichloride) were added. Stirring 2~U243 l was then carried out for 1.5 h, wherein the flask contents turned red-brown. Then 121.2 g of white oil (Witco Parol~) were added, in order to attain an approximately 25% suspension.
The toluene was completely distilled off at a maximum of 45~C and a vacuum of up to 0.1 mbar in 6 h. A red-brown, highly viscous suspension was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 5.25%
Zr: 0.27%
Example 11 Metallocene/methylaluminoxane/silica suspension in white oil 52.4 g of silica (SYLOPOL~ 2104) on which was supported methylaluminoxane, with an aluminum content of 23.8~, was fed under a protective nitrogen atmosphere, and 3.14 g -EURECEN~ 5036 were added.
111.1 g white oil (Witco Parol~) were added to this mixture of solids and stirred for over 2 h. A
viscous, curry-colored 33~ suspension was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 7.48%
22~u24~
l Zr: 0.38~ -Comparative examples In Comparative Examples 12 and 13 a commercial MAO solution, sold by the Witco Company, Bergkamen, Germany, under the trade name EURECEN~ Al 5100/lOT, was used and together with the other catalyst components, metered directly into the polymerization reactor. The concentrations of the active catalyst material can be seen in Tables I and II.
Polymerization results Polymerization results and analytical data for homogeneous formulations 3o 2 L ~ U 2 43 Table I *
Example Formulation %Al, ~Zr in Productivity of the Formulation formulation, kg PE/mol Zr h l MAO in Paroll~ 13.4; o.00 30552 2 MA0 in Petroleum 12.0; 0.00 29880 Jelly'~
3 MA0 (solid) in 26.1; 0.00 35256 paraffin 4 MA0 in Paroll~ 30.1 0.00 55584 MAO in Va~eline 12.3; 0.00 25704 (S~ nn~ 1) 6 MAO/ 14.11 0.77 3456 metallocene2~
prepared-in Parol and polynierized immediately 7 MA0/ 14.11 0.77 29964 metallocene2l, prepared in Parol and polymerized after 24 h 8 MA0/ 14.11 0.77 57288 metallocene2~, prepared in Parol and polymerized after 48 h 12 MA0 in toluene 4.84; 0.00 29328 (Comparative Example)l) 1) = Bis(n-butylcyclopentadienyl)zirconium dichloride 2) = Ethylene-1.2-bi~indenyl) zirconium dichloride (MA0: 900 g/mol; metallocene, ab~. conc. conc. 1.25 x 10-6 mol Zr;
Al:Zr=1000:1); 900 mL toluene; 30~C in~ide temperature; 4 bar ethene; 1000 rpm; 20 min) 3o 2~0~)24~
-1 Polymerization results and analytical data for heterogeneous formulations Table II
Example Formulation ~Al ~Zr Productivity kg PE/mol Zr h 9 MAO/SiO2/ 7.17 0.33 4200 Metallocene, suspended in Parol2 ~ .
MAO/SiO2/ 5.25 0.27 2228 Metallocene, prepared in Parol2~ .
11 MAo/sio2/ 7.48 0.38 1081 Metallocene, prepared in Parol2) 13 MAO/SiO2/ 5.2S 0.27 688 Metallocene, suspended in toluene (Comparative Example)2) 1) = Bis(n-butylcycolpentadienyl)zirconium dichloride 2) = Ethylene-1,2-bis(indenyl)zirconium dichloride (MAo/Sio2, 23.8~ Al; metallocene abs. conc. 1.25 x 10-6 mole Zr; triisobutylaluminum (Al:Zr=800:1); 900 mL
toluene; 40~C inside temperature; 4 bar ethene; 1000 rpm; 20 min) 3o
Porous, partially polymeric compounds, such as polyethylene, polypropylene, polystyrene, and-sugar derivatives (starch, amylose, cyclodextrins), can be taken into consideration as organic carrier materials that can be used in accordance with the invention.
To prepare the formulations of the--invention, in accordance with the method of the invention, there are basically different possibilities, for example:
~20~)243 1 M1) Preparat_on of the metallocene-based catalyst system in the dispersing /suspending medium or solvent (paraffin), in accordance with the lnvention.
M2) Dissolution, suspension, or dispersion of already isolated metallocene-based catalyst components in the dispersing medium or solvent (paraffin), in accordance with the invention M3) Mixing of nonaromatic solvent or dispersing agent with a solution of the metallocene-based catalyst components and subsequent separation of the solvent by means of distillation, thus obtaining the solutions, suspensions, or dispersions, in accordance with the invention.
To prepare the formulations, the catalyst components can be used in pure form as well a~ on a suitable support material. If the catalyst components are used in pure ~orm, the support material and auxiliaries, additives, and accessory agents can be added to the processing possibilities M1)-M3) at any time.
The following examples illustrate the synthesis of the claimed metallocene-catalyst systems and their testing in the polymerization.
22 ~J~2i~3 --ll--1 Synthesis Examples Example 1 Methylaluminoxane in Witco Parol~ (trade name of Witco Netherlands) 402 g of a toluene solution of MA0 (Al total, 13.2%; Al as TMA, 3.19~) and 219 g Witco Parol~
were fed under nitrogen atmosphere to a 1-~ flask, equipped with a thermometer and stirrer that moves around the edges. The flask contents were heated in an oil bath to a m~;ml~m 32~C and a vacuum was applied. The distilled-off toluene was condensed in a low-temperature trap. It was possible to strengthen the vacuum with the declining toluene content of the suspension. Toluene residues were distilled off at cl mbar for 3 h.
A viscous and milky-turbid suspension was obtained. The suspension wa~ neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 13.4%
Al as TMA: 1.5 Example 2 Methylaluminoxane in Witco Petroleum Jelly Snowwhite MD~ (Vaseline, Witco Netherlands) 3o ~ ~ ù~2~3 l 130.1 g of a toluene solution of MA0 (Al total, 13.2; Al as TMA, 3.19%) and 85.1 g White Petroleum Jelly Snowwhite MD~ were fed into a 500-mL
Schlenk tube, equipped with a stirrer, under a protective nitrogen atmosphere. After heating to 55-60~C in an oil bath, the mixture became homogeneous.
The toluene was distilled off in a vacuum and condensed in a low-temperature trap. The vacuum was continuously increased to below 1 mbar, and the bath temperature was maintained at a maximum of 65~C.
After complete ~e-,loval of the toluene, a colorless, homogeneous, waxlike mass was obtained, which flowed at approximately 60~C.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 12.0%
Al as TMA: 1.9%
ExamPle 3 Methylaluminoxane in paraffin wax 33.5 g Methylaluminoxane (solid) and 16.8 g paraffin (Terhell 5605~, Schumann Company) were heated under nitrogen in a round-bottomed flask with a stirrer that moves around the edges. With a bath temperature of 65-70~C, a turbid melt was obtained.
The melt was allowed to solidify while stirring and then the melt was dissolved from the walls of the ~ ' IJ~.i243 .
1 flask. After cooling externally with dry ice, it was possible to comminute the solid to a fine grain solid which could be poured.
The powder, containing approximately 66%
MA0, was not pyrophoric or self-igniting.
Al total: 26.1 Al as TMA: 3.5 Example 4 Methylaluminoxane in Witco Parol~
26.3 g of a finely pulverized MA0 solid (Al total, 39.2%) were stirred with 7.3 g white oil Witco Parol~ under a protective argon atmosphere. A
colorless, waxlike mass was obtained.
The powder containing approximately 78~ MA0 was not pyrophoric or self-igniting and exhibited only a moderate gas development upon contact with water.
Placed on moist filter paper, carbonization without self-ignition was observed.
Al total: 30.1 Al as TMA: 3.6 Example 5 Dispersion of methylaluminoxane in petrolatum (Vaseline) Under a protective nitrogen atmosphere, 125 g of a toluene solution of MA0 (Al total, 13.2~; Al as 2~)2~3 l TMA, 3.19%) and 78.5 g petrolatum, white, German Pharmacopoeia 10, VARH AB (Sch*m~nn Company) were fed into a 500-mL Schlenk tube, equipped with a stirrer.
After heating to 55-60~, the toluene was distilled off and condensed in a low-temperature trap. The vacuum was continuously increased to below 1-mbar, and the bath temperature was maintained at a m~;m1]m 65~C.
After complete le...Jvdl of the toluene, a colorless, homogeneous dispersion was obtained, which could flow at above approximately 60~C.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 12.3 15 Al as TMA: 1.6 Example 6 Suspension of methylaluminoxane and metallocene in 20 white oil - 60.5 g of a toluene solution of MA0 (Al content, 13.2~; Al as TMA, 3.19~) were fed into a stirring apparatus under a protective argon 25 atmosphere. 2.0 g EURECEN~ 5036 (trade name of the Witco Company, Bergkamen, Germany - 1,2-ethylenebis(1-indenyl)zirconium dichloride) were added to this solution, and stirring was carried out for 30 min. 39 g white oil Witco Parol~ were metered into this dark-brown solution and heated to 40~C. The toluene was 2~ 1ulu243 l distilled off under a vacuum of up to 0.1 mbar and condensed in a low-temperature trap.
56.6 g of a brown, waxli~e catalyst mass was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 14.11%
Zr: 0.77%
Example 7 The procedure was carried out as in Example 6. Before use in the polymerization, the mixture was subjected to a 24-h aging process in toluene.
Example 8 The procedure was carried out as in Example 6. Before use in-the polymerization, the mixture was subjected to a 48-h aging process in toluene.
Example 9 Suspension of supported MA0/metallocene/silica catalyst system in Witco Parol~
23 g of a supported catalyst system (TA
02954, research product from the Witco Company; Al 22 i~u2~3 l content, 23.9~, Zr content 1.1~) were stirred with 53.7 g while oil Witco Parol~ in a stirred vessel under a protective argon atmosphere. A dark-brown suspension was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 7.17 Zr total: 0.33 Example 10 Metallocene/methylaluminoxane/silica suspension in white oil 203.5 g of a 10~ solution of methylaluminoxane in toluene (Al content, 5.0~) were introduced into an apparatus suitable for working under a protective argon atmosphere, with stirrer, thermometer, reflux condenser, and metering of solids.
18.8 g Silica (SYLOPOL 2104~, ~race Company, with 5% water content) were thoroughly shaken with 1.5 g distilled water for approximately 10 min, poured into the solids meter, and slowly added to the stirred methylalllm;noxane solution. With gas development (methane gas), the temperature rose to 65~C. After the end of the addition, stirring was carried out - until room temperature was once again reached, and then 2.44 g EURECEN~ 5036 1,2-ethylenebis(1-indenyl)zirconium dichloride) were added. Stirring 2~U243 l was then carried out for 1.5 h, wherein the flask contents turned red-brown. Then 121.2 g of white oil (Witco Parol~) were added, in order to attain an approximately 25% suspension.
The toluene was completely distilled off at a maximum of 45~C and a vacuum of up to 0.1 mbar in 6 h. A red-brown, highly viscous suspension was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 5.25%
Zr: 0.27%
Example 11 Metallocene/methylaluminoxane/silica suspension in white oil 52.4 g of silica (SYLOPOL~ 2104) on which was supported methylaluminoxane, with an aluminum content of 23.8~, was fed under a protective nitrogen atmosphere, and 3.14 g -EURECEN~ 5036 were added.
111.1 g white oil (Witco Parol~) were added to this mixture of solids and stirred for over 2 h. A
viscous, curry-colored 33~ suspension was obtained.
The suspension was neither pyrophoric nor self-igniting; slight gas generation took place on addition of water.
Al total: 7.48%
22~u24~
l Zr: 0.38~ -Comparative examples In Comparative Examples 12 and 13 a commercial MAO solution, sold by the Witco Company, Bergkamen, Germany, under the trade name EURECEN~ Al 5100/lOT, was used and together with the other catalyst components, metered directly into the polymerization reactor. The concentrations of the active catalyst material can be seen in Tables I and II.
Polymerization results Polymerization results and analytical data for homogeneous formulations 3o 2 L ~ U 2 43 Table I *
Example Formulation %Al, ~Zr in Productivity of the Formulation formulation, kg PE/mol Zr h l MAO in Paroll~ 13.4; o.00 30552 2 MA0 in Petroleum 12.0; 0.00 29880 Jelly'~
3 MA0 (solid) in 26.1; 0.00 35256 paraffin 4 MA0 in Paroll~ 30.1 0.00 55584 MAO in Va~eline 12.3; 0.00 25704 (S~ nn~ 1) 6 MAO/ 14.11 0.77 3456 metallocene2~
prepared-in Parol and polynierized immediately 7 MA0/ 14.11 0.77 29964 metallocene2l, prepared in Parol and polymerized after 24 h 8 MA0/ 14.11 0.77 57288 metallocene2~, prepared in Parol and polymerized after 48 h 12 MA0 in toluene 4.84; 0.00 29328 (Comparative Example)l) 1) = Bis(n-butylcyclopentadienyl)zirconium dichloride 2) = Ethylene-1.2-bi~indenyl) zirconium dichloride (MA0: 900 g/mol; metallocene, ab~. conc. conc. 1.25 x 10-6 mol Zr;
Al:Zr=1000:1); 900 mL toluene; 30~C in~ide temperature; 4 bar ethene; 1000 rpm; 20 min) 3o 2~0~)24~
-1 Polymerization results and analytical data for heterogeneous formulations Table II
Example Formulation ~Al ~Zr Productivity kg PE/mol Zr h 9 MAO/SiO2/ 7.17 0.33 4200 Metallocene, suspended in Parol2 ~ .
MAO/SiO2/ 5.25 0.27 2228 Metallocene, prepared in Parol2~ .
11 MAo/sio2/ 7.48 0.38 1081 Metallocene, prepared in Parol2) 13 MAO/SiO2/ 5.2S 0.27 688 Metallocene, suspended in toluene (Comparative Example)2) 1) = Bis(n-butylcycolpentadienyl)zirconium dichloride 2) = Ethylene-1,2-bis(indenyl)zirconium dichloride (MAo/Sio2, 23.8~ Al; metallocene abs. conc. 1.25 x 10-6 mole Zr; triisobutylaluminum (Al:Zr=800:1); 900 mL
toluene; 40~C inside temperature; 4 bar ethene; 1000 rpm; 20 min) 3o
Claims (12)
1. A method for producing a homogeneous mixture consisting essentially of an optionally supported catalyst system consisting of at least one metallocene and at least one cocatalyst, and a formulation medium, comprising A) preparing the catalyst system directly in the formulation medium, or B) preparing separately the catalyst system and then suspending, dispersing or dissolving it in the formulation medium, or C) introducing a solution of the catalyst system in a low-boiling solvent into the formulation medium in a first step, and in a second step removing the low-boiling solvent, D) wherein the homogeneous mixture also optionally contains one or more of inorganic or organic carrier materials, auxiliary agents and additives.
2. A method according to Claim 1, wherein one or more organoaluminum compounds are used as cocatalyst.
3. A method according to Claim 1, wherein one or more aluminoxanes are used as cocatalyst.
4. A method according to Claim 1, wherein one or more organoboron compounds are used as cocatalyst.
5. A method according to Claim 1, wherein methylaluminoxane is used as cocatalyst.
6. A method according to Claim 1, wherein one or more metallocenes of general formula (1) are used as catalyst:
Q(CpRa)(Cp'R'a')M(x)n (1) wherein Cp is a cyclopentadienyl, indenyl, or fluorenyl radical, R and R' are the same or different and each is a C1-C10 alkyl, phosphine, amine, C1-C10 alkyl ether, or C6-C10 aryl ether group, 0 ~ a ~4 and 0~ a'~4, Cp' is one of the groups Cp or Cp' is -NR"-wherein R" is an alkyl or aryl radical in which a is 1, Q is a single bridge or multibridge between Cp and Cp', wherein R1 and R2 are the same or different and each is a hydrogen atom, a C1-C10alkyl group, or a C6-C10 aryl group, and Z denotes carbon, silicon, or germanium, in which b is 0, 1, 2, or 3, M is a transition metal of any of the groups 3-6 of the Periodic Table (IUPAC notation), X is halogen, and n is the oxidation number of M, reduced by 2.
Q(CpRa)(Cp'R'a')M(x)n (1) wherein Cp is a cyclopentadienyl, indenyl, or fluorenyl radical, R and R' are the same or different and each is a C1-C10 alkyl, phosphine, amine, C1-C10 alkyl ether, or C6-C10 aryl ether group, 0 ~ a ~4 and 0~ a'~4, Cp' is one of the groups Cp or Cp' is -NR"-wherein R" is an alkyl or aryl radical in which a is 1, Q is a single bridge or multibridge between Cp and Cp', wherein R1 and R2 are the same or different and each is a hydrogen atom, a C1-C10alkyl group, or a C6-C10 aryl group, and Z denotes carbon, silicon, or germanium, in which b is 0, 1, 2, or 3, M is a transition metal of any of the groups 3-6 of the Periodic Table (IUPAC notation), X is halogen, and n is the oxidation number of M, reduced by 2.
7. A method in accordance with Claim 6 wherein M is Zr or Hf, and X is Cl or Br.
8. A method in accordance with Claim 1 or 6, wherein the catalyst component is one or more metallocenes selected from the group consisting of (bis(cyclopentadienyl))zirconium dichloride, (bis(methylcyclopentadienyl))zirconium dichloride, (bis(n-propylcyclopentadienyl))zirconium dichloride, (bis(isobutylcyclopentadienyl))zirconium dichloride, (bis(cyclopentylcyclopentadienyl))zirconium dichloride, (bis(benzylcyclopentadienyl))zirconium dichloride, (bis(octadecylcyclopentadienyl))zirconium dichloride, (bis(n-butylcyclopentadienyl))titanium dichloride, (bis(n-butylcyclopentadienyl))zirconium dichloride, (bis(n-butylcyclopentadienyl))hafnium dichloride, (bis(indenyl))zirconium dichloride, (bis(indenyl))dimethylzirconium, (bis(tetrahydroindenyl))zirconium dichloride, (1,2-ethylenebis(indenyl))zirconium dichloride, (1,2-ethylenebis(indenyl))hafnium dichloride, (1,2-ethylenebis(tetrahydroindenyl))zirconium dichloride, (dimethylsilylbis(1H-inden-1-yl))zirconium dichloride, and (dimethylsilylbis(1H-inden-1-yl))hafnium dichloride.
9. A method according to Claim 1 wherein the formulation medium is a hydrocarbon with a boiling point above 150°C and a viscosity of at least 1 Pa.sec at 25°C.
10. A homogeneous mixture produced according to the method of claim 1.
11. A homogeneous mixture consisting essentially of an optionally supported catalyst system consisting of at least one metallocene and at least one cocatalyst, and a formulation medium.
12. A homogeneous mixture according to Claim 11 wherein said formulation medium is a hydrocarbon with a boiling point above 150°C and a viscosity of at least 1 Pa.sec at 25°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96104295A EP0798315B1 (en) | 1996-03-19 | 1996-03-19 | Process for preparing highly active, stable metallocene catalyst systems, and catalyst compositions prepared according therewith |
| EP96104295.9 | 1996-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2200243A1 true CA2200243A1 (en) | 1997-09-19 |
Family
ID=8222573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002200243A Abandoned CA2200243A1 (en) | 1996-03-19 | 1997-03-18 | Method for producing highly active, stable metallocene catalyst systems,and formulations produced thereby |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0798315B1 (en) |
| JP (1) | JP2941731B2 (en) |
| KR (1) | KR100512507B1 (en) |
| AT (1) | ATE159734T1 (en) |
| CA (1) | CA2200243A1 (en) |
| DE (1) | DE59600039D1 (en) |
| ES (1) | ES2111407T3 (en) |
| NO (1) | NO312072B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255245B1 (en) | 1998-06-16 | 2001-07-03 | Bayer Aktiengesellschaft | Process for the preparation of supported polymerization catalyst systems and use thereof in the homo-and co-polymerization of unsaturated monomers |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19756265A1 (en) * | 1997-12-18 | 1999-06-24 | Targor Gmbh | Polymerization process with a decomposition-insensitive metallocene catalyst |
| KR100304048B1 (en) * | 1999-07-02 | 2001-11-14 | 유현식 | Metallocene Catalysts for Polymerization of Styrene and Method of Polymerization Using the Same |
| WO2002050134A1 (en) | 2000-12-19 | 2002-06-27 | Sunallomer Ltd. | Olefin polymerization catalyst, catalyst component for olefin polymerization, method of storing these, and process for producing olefin polymer |
| JP2004516363A (en) | 2000-12-22 | 2004-06-03 | バセル ポリオレフィン ジーエムビーエイチ | Catalyst component for olefin polymerization |
| US6777367B2 (en) * | 2001-02-13 | 2004-08-17 | Fina Technology, Inc. | Method for the preparation of metallocene catalysts |
| US6777366B2 (en) * | 2001-02-13 | 2004-08-17 | Fina Technology, Inc. | Method for the preparation of metallocene catalysts |
| JP2007528924A (en) * | 2004-03-12 | 2007-10-18 | バセル ポリオレフィン ジーエムビーエイチ | Catalyst system for olefin polymerization |
| CA2749835C (en) | 2011-08-23 | 2018-08-21 | Nova Chemicals Corporation | Feeding highly active phosphinimine catalysts to a gas phase reactor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026797A (en) * | 1987-10-22 | 1991-06-25 | Mitsubishi Petrochemical Co., Ltd. | Process for producing ethylene copolymers |
| WO1991003500A1 (en) * | 1989-09-08 | 1991-03-21 | Fina Research S.A. | Catalyst and process for the polymerization of olefins |
| TW337527B (en) * | 1992-01-24 | 1998-08-01 | Hoechst Ag | Catalyst for the polymerization of olefins, process for the preparation thereof, and use thereof |
| US5393851A (en) * | 1992-05-26 | 1995-02-28 | Fina Technology, Inc. | Process for using metallocene catalyst in a continuous reactor system |
-
1996
- 1996-03-19 ES ES96104295T patent/ES2111407T3/en not_active Expired - Lifetime
- 1996-03-19 EP EP96104295A patent/EP0798315B1/en not_active Expired - Lifetime
- 1996-03-19 DE DE59600039T patent/DE59600039D1/en not_active Expired - Lifetime
- 1996-03-19 AT AT96104295T patent/ATE159734T1/en active
-
1997
- 1997-03-12 JP JP9056752A patent/JP2941731B2/en not_active Expired - Lifetime
- 1997-03-18 NO NO19971254A patent/NO312072B1/en not_active IP Right Cessation
- 1997-03-18 CA CA002200243A patent/CA2200243A1/en not_active Abandoned
- 1997-03-18 KR KR1019970009102A patent/KR100512507B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255245B1 (en) | 1998-06-16 | 2001-07-03 | Bayer Aktiengesellschaft | Process for the preparation of supported polymerization catalyst systems and use thereof in the homo-and co-polymerization of unsaturated monomers |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2111407T3 (en) | 1998-03-01 |
| JPH09328508A (en) | 1997-12-22 |
| KR100512507B1 (en) | 2006-02-08 |
| NO312072B1 (en) | 2002-03-11 |
| JP2941731B2 (en) | 1999-08-30 |
| NO971254L (en) | 1997-09-22 |
| KR970065548A (en) | 1997-10-13 |
| DE59600039D1 (en) | 1997-12-11 |
| ATE159734T1 (en) | 1997-11-15 |
| NO971254D0 (en) | 1997-03-18 |
| EP0798315B1 (en) | 1997-10-29 |
| EP0798315A1 (en) | 1997-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |