CA2017190C - Process for the preparation of ethylene polymers - Google Patents
Process for the preparation of ethylene polymersInfo
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- CA2017190C CA2017190C CA002017190A CA2017190A CA2017190C CA 2017190 C CA2017190 C CA 2017190C CA 002017190 A CA002017190 A CA 002017190A CA 2017190 A CA2017190 A CA 2017190A CA 2017190 C CA2017190 C CA 2017190C
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- metallocene
- fluorenyl
- ethylene
- dichloride
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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
- C08F10/02—Ethene
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 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
- C08F4/63927—Component covered by group C08F4/62 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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Process for the preparation of ethylene polymers The preparation of polyethylene and ethylene-1-olefin copolymers in the suspension or gas phase process with the aid of metallocene/aluminoxane catalysts whose metallocene component is a bridged biscyclopentadienyl complex offers particular advantages.
Depending on the structure of the complex, the use of these complexes gives, with high activity, products in a very broad molecular-weight range and permits the production of very varied grain morphologies of the products, such as high and low bulk density, extremely small and extremely large mean grain diameters and various grain shapes. The variety of grain morphologies which can be achieved opens up various possibilities for the use of such polyethylene powders in sintering processes.
Depending on the structure of the complex, the use of these complexes gives, with high activity, products in a very broad molecular-weight range and permits the production of very varied grain morphologies of the products, such as high and low bulk density, extremely small and extremely large mean grain diameters and various grain shapes. The variety of grain morphologies which can be achieved opens up various possibilities for the use of such polyethylene powders in sintering processes.
Description
HOECHST AKTIENGESELLSCHAFT HOE 89/F 155 Dr ~ ~/~51~ ~~
Description Process for the preparation of ethylene polymers The present invention relates to a process for the preparation of polyethylene and ethylene-1-olefin copoly-mers of various molecular weight ranges with the aid of metallocene/aluminaxane catalysts.
.A process for the preparation of polyethylene with the aid of metallocene/aluminoxane catalysts in toluene as suspending agent has already been described [cf.
EP 69,951]. The molecular weights achieved for the polymers are relatively low. No data is given on the morphology of the polymers.
Furthermore, a comparable process using a high-boiling hydrocarbon as suspending agent has been disclosed (cf.
EP 170,059). However, the catalyst activities are moder-ate, and the bulk densities achis:ved for the polymer are between 0.15 and 0.18 g/cm3.
Furthermore, processes have been described for the preparation of polyethylene and ethylene-1-olefin copoly-mers with the aid of metallocene/~aluminoxane catalysts by polymerization in the gas phase [cf. EP 206,794, 285,443 and 294,942). Here too, only moderately high molecular weights of the polymers and in most cases only poor activities of the catalysts are achieved.
It is common to all the abovementioned processes that, as the metallocene, unbridged biscyclopentadienylzirconium complexes are employed in which the cyclopentadienyl radicals are substituted or unsubstituted, and the metal-~0 locene is either employed as such in the polymerization or has been linked to an inert support by appropriate preliminary reaction steps.
Description Process for the preparation of ethylene polymers The present invention relates to a process for the preparation of polyethylene and ethylene-1-olefin copoly-mers of various molecular weight ranges with the aid of metallocene/aluminaxane catalysts.
.A process for the preparation of polyethylene with the aid of metallocene/aluminoxane catalysts in toluene as suspending agent has already been described [cf.
EP 69,951]. The molecular weights achieved for the polymers are relatively low. No data is given on the morphology of the polymers.
Furthermore, a comparable process using a high-boiling hydrocarbon as suspending agent has been disclosed (cf.
EP 170,059). However, the catalyst activities are moder-ate, and the bulk densities achis:ved for the polymer are between 0.15 and 0.18 g/cm3.
Furthermore, processes have been described for the preparation of polyethylene and ethylene-1-olefin copoly-mers with the aid of metallocene/~aluminoxane catalysts by polymerization in the gas phase [cf. EP 206,794, 285,443 and 294,942). Here too, only moderately high molecular weights of the polymers and in most cases only poor activities of the catalysts are achieved.
It is common to all the abovementioned processes that, as the metallocene, unbridged biscyclopentadienylzirconium complexes are employed in which the cyclopentadienyl radicals are substituted or unsubstituted, and the metal-~0 locene is either employed as such in the polymerization or has been linked to an inert support by appropriate preliminary reaction steps.
It has now been found that the preparation of polyethy-lene and ethylene-1-olefin copolymers by suspension or gas-phase processes with the aid of metallocene/alumin-oxane catalysts whose metallocene component is a bridged biscyclopentadienyl complex offers important advantages.
The invention thus relates to a process for the prepara-tion of ethylene polymers by polymerization of ethylene or copolymerization of ethylene with 1-olefins having 3 to 20 carbon atoms at a temperature of from -60 to 200°C
and a pressure of from 0.5 to 200 bar in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a metallocene as the transition-metal component and an aluminoxane of the formula II
9 Al - O A1 - C - A1~ 9 (II) R _n ~ R
for the linear type and/or of the formula III
Rg (III) AZ - -*2 for the cyclic type, where, in the formulae TI and III, R9 is a C1-C6-alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition-metal component is a compound of the formula I
o Rl R5 1K1 / ( I ) i .e R2 R~
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1 and Rz are identical or different and are a hydrogen atom, a halogen atom, a C1--Clo-alkyl group, a C1-C~o-alkoxy group, a C6-Clo-aryl group, a C6-Clo-aryloxy group, a CZ-Coo-alkenyl groug, a C~-C4o-arylalkyl group, a C~-C44-alkylaryl group or a C~-C4o-arylalkenyl groug, R3 and R° are identical or different and are a mono-nuclear or polynuclear hydrocarbon radical which, with the central atom M1, is able to form a sandwich structure, R5 i s R6 Rf R6 R~ R~
1 1 I i 1 MZ , C , C M2 C
P P P
I I 1 i v _ M2 C M2 _ . _ M2 .. D _ M2 _ R~ R8 R7 R~ R~
P
Rf R6 O _ M2 _ ~ _ M2 _ CR 8 R7 . R7 2 =$Rs, =A1R6, -Ge-, -Sri-, -0-, -S-, =S0, =SOZ, =NRs, =CO, =PRs or =P ( O ) Rs, where Rs, R' and Ro are identi-cal or different and are a hydrogen atom, a halogen atom, a C1-Clo-alkyl group, a C1-Clo-fluoroalkyl group, a C6-Clo-fluoroaryl group, a C6-Clo-aryl group, a Cl--Clo-alkoxy group, a CZ-Clo-alkenyl group, a C~-C4o-arylalkyl group, a Ce-C4o-arylalkenyl group or a C~-C4o-alkylaryl group, or R6 and R' or Rs and Rg, in each case with the atoms connecting them, form a ring, MZ is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or 5.
The catalyst to be used for the process according to the invention comprises an aluminoxane and a metallocene of the formula 1 I
R' M1 r (T).
i ~ R2 ~4 R
In the formula I, M1 is a metal selected from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium.
R1 and Rz are identical or different and are a hydrogen atom, a C1-Clo-, preferably Cl-C3-alkyl group, a Cl-Clo-, preferably C1-C3-alkoxy group, a C6-Clo-, preferably C~-C$-aryl group, a C6-Clo-, preferably C6-C8-aryloxy group, a Cz-Clo-, preferably Cz-C,,-alkenyl group, a C~-C~,o-, prefer-ably C7-Clo-arylalkyl group, a C~-C4o-, preferably C7-Clz-alkylaryl group, a Ce-C4o-, preferably Ce-Clz-arylalkenyl group or a halogen atom, preferably chlorine.
R3 and R" are identical or different and are a mononuclear or polynuclear hydrocarbon radical which, together with the central atom Ml, is able to form a sandwich structure.
R3 and R~ are preferably cyclopentadienyl, indenyl, tetra-hydroindenyl or fluorenyl, it also being possible for the basic structures to carry additional substituents.
RS is a mono- or polymembered bridge which links the radicals R3 and R° and is R~' R~' Rf R$ R6 i w t 1 M2 , C , - C M2 C - , R7 R~ R7 R8 R7 p P P
Rs ~Ra ' .RS R6 R6 _ M2 C M2 _ . _ M2 _ O _ M2 _ R7 R~ R~ R' R~
P
The invention thus relates to a process for the prepara-tion of ethylene polymers by polymerization of ethylene or copolymerization of ethylene with 1-olefins having 3 to 20 carbon atoms at a temperature of from -60 to 200°C
and a pressure of from 0.5 to 200 bar in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a metallocene as the transition-metal component and an aluminoxane of the formula II
9 Al - O A1 - C - A1~ 9 (II) R _n ~ R
for the linear type and/or of the formula III
Rg (III) AZ - -*2 for the cyclic type, where, in the formulae TI and III, R9 is a C1-C6-alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition-metal component is a compound of the formula I
o Rl R5 1K1 / ( I ) i .e R2 R~
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1 and Rz are identical or different and are a hydrogen atom, a halogen atom, a C1--Clo-alkyl group, a C1-C~o-alkoxy group, a C6-Clo-aryl group, a C6-Clo-aryloxy group, a CZ-Coo-alkenyl groug, a C~-C4o-arylalkyl group, a C~-C44-alkylaryl group or a C~-C4o-arylalkenyl groug, R3 and R° are identical or different and are a mono-nuclear or polynuclear hydrocarbon radical which, with the central atom M1, is able to form a sandwich structure, R5 i s R6 Rf R6 R~ R~
1 1 I i 1 MZ , C , C M2 C
P P P
I I 1 i v _ M2 C M2 _ . _ M2 .. D _ M2 _ R~ R8 R7 R~ R~
P
Rf R6 O _ M2 _ ~ _ M2 _ CR 8 R7 . R7 2 =$Rs, =A1R6, -Ge-, -Sri-, -0-, -S-, =S0, =SOZ, =NRs, =CO, =PRs or =P ( O ) Rs, where Rs, R' and Ro are identi-cal or different and are a hydrogen atom, a halogen atom, a C1-Clo-alkyl group, a C1-Clo-fluoroalkyl group, a C6-Clo-fluoroaryl group, a C6-Clo-aryl group, a Cl--Clo-alkoxy group, a CZ-Clo-alkenyl group, a C~-C4o-arylalkyl group, a Ce-C4o-arylalkenyl group or a C~-C4o-alkylaryl group, or R6 and R' or Rs and Rg, in each case with the atoms connecting them, form a ring, MZ is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or 5.
The catalyst to be used for the process according to the invention comprises an aluminoxane and a metallocene of the formula 1 I
R' M1 r (T).
i ~ R2 ~4 R
In the formula I, M1 is a metal selected from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium.
R1 and Rz are identical or different and are a hydrogen atom, a C1-Clo-, preferably Cl-C3-alkyl group, a Cl-Clo-, preferably C1-C3-alkoxy group, a C6-Clo-, preferably C~-C$-aryl group, a C6-Clo-, preferably C6-C8-aryloxy group, a Cz-Clo-, preferably Cz-C,,-alkenyl group, a C~-C~,o-, prefer-ably C7-Clo-arylalkyl group, a C~-C4o-, preferably C7-Clz-alkylaryl group, a Ce-C4o-, preferably Ce-Clz-arylalkenyl group or a halogen atom, preferably chlorine.
R3 and R" are identical or different and are a mononuclear or polynuclear hydrocarbon radical which, together with the central atom Ml, is able to form a sandwich structure.
R3 and R~ are preferably cyclopentadienyl, indenyl, tetra-hydroindenyl or fluorenyl, it also being possible for the basic structures to carry additional substituents.
RS is a mono- or polymembered bridge which links the radicals R3 and R° and is R~' R~' Rf R$ R6 i w t 1 M2 , C , - C M2 C - , R7 R~ R7 R8 R7 p P P
Rs ~Ra ' .RS R6 R6 _ M2 C M2 _ . _ M2 _ O _ M2 _ R7 R~ R~ R' R~
P
R~ RG
M2 _ ~ _ M2 _ CR$ _ =BRs, =A1R6, -Ge-, -Sn-, -0-, -S-, =SO, =SO2, =IdRsr =C0, =PR6 or =P ( O ) R6, where R6, R' and R8 are identi-cal or different and are a hydrogen atom, a halogen atom, preferably chlorine, a C1-Clo-, preferably C1-C3-alkyl group, in particular a methyl group, a C1-Clo-fluoroalkyl group, preferably a CF3 group, a C6-Clo-fluoroaryl group, preferably a pentafluorophenyl group, a C6-Clo-, preferably C6-Ce-aryl group, a Cl_ Clo-. preferably Cl-C;,-alko~cy group, in particular a methoxy group, a GZ-Clo-, preferably CZ-C~-alkenyl group, a C~-C4o-, preferably C~-Clo-aryl alkyl group, a Ce-C4o-, preferably C8-C12-arylalkenyl group or a C~-C4o-, preferably C~-C12-alkylaryl group, or R6 and R' or R6 and Ro in each case, together with the atoms connecting them, form a ring, MZ is silicon, germanium or ti;n, preferably silicon or germanium, and p is the number 1, 2, 3, ~ or 5.
Particularly preferred metallocenes are:
rac-dimethylsilylbis(1-indenyl)zirconium dichloride, rac-diphenylsilyibis(1-indenyl)zirconium dichloride, 1-silacyclobutylbis(1'-indenyl)zirconium dichloride, rac-~dimethylsilylbis(1-(3-methylindenyl))ziroonium dichloride, rac-1,1,2,2-tetramethyldisilaethylenebis(1'-indenyl)zir-conium dichloride, dimethylsilylbis(1-(3-trimethylsilyl)cyclopentadienyl)-zirconitun dichloride, and diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride.
The above-described metallocenes can be prepared by the general reaction scheme below:
_ H2R3+butylLi -~ HR~Li HR3-R5-R4H 2 b_utylLi~, HzR4+butylLi -~ HR'~Li ' LiR3-R5-R~Li tilltil i e' C1 ~ I / R1 ~~ p ~1 R5 M1 _ R1L ~. R5 ~ ~ R2~ R5 M1 a \Cl ~ 1 Cl -~ , ~ R2 R4 R~ . R~
(X = C1, Bx, I, O-tosyl) -- l _ or H2R3 + butylLi -~ HR3Li R6 R7 ~.-R4H
~ C / a, _HR3Li s R~R~C
R~' b, HAD \ R3H
2 butylLi a R
(R6R~C \ ]Lia R ~ ~ ~ ~,C1 R7/ \ ~ ~ C1 ~4 R
RlLi R ~ ~ s /R1 1~\ ~ ~ 1/ R1 C Ml R~Li~ ~C M~
R~ \ ~ ~ cl R~ \ ~ aRz Rg R4 The cocatalyst is an aluminoxane of the formula II
R~ Rg R~
\A1 - 0 ,~A1 - O A1 ~ ( II ) R~/ ~ n ~R~
for the linear type and/or of the formula III
_8_ A1 - O (III) n+2 for the cyclic type. In these formulae, R9 is a C1-Cs-alkyl group, preferably methyl, ethyl or isobutyl, butyl or neopentyl, or phenyl or benzyl. Methyl is particularly preferred. n is an integer from 2 to 50, preferably 5 to 40. However, the exact structure of the aluminoxane is not known.
The aluminoxane can be prepared in various ways.
One possibility is the careful addition of water to a dilute solution of a trialkylaluminum by introducing the solution of the trialkylaluminum, preferably trimethyl-aluminum, and the water in each case in small portions into an initially introduced larger amount of an inert solvent and between each portion awaiting the end of the evolution of gas.
In anothex process, finely powdered copper sulfate pentahydrate is slurried in toluene, and, in a glass flask under an inert gas at about -20°C, sufficient trialkylaluminum is added so that about 1 mole of CuS0,,.5H20 is available for each 4 A1 atoms. lifter slow hydrolysis with elimination of alkane, the reaction mixture is left at room temperature for 24 to 48 hours, cooling possibly being needed to ensure that the tempera-ture does not exceed 30°C. The aluminoxane dissolved in the toluene is subsequently filtered off from the copper sulfate, and the solution is evaporated in vacuo. It is assumed that the low-molecular-weight aluminoxanes condense in these preparation processes to form higher oligomers with elimination of trialkylaluminum.
Furthermore, aluminoxanes are obtained if trialkylalumi-num, preferably trimethylaluminum, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or g _ toluene, is reacted at a temperature of from -20 to 100°C
with aluminum salts, preferably aluminum sulfate, con-taining water of crystallization. In this case, the volume ratio between the solvent and the alkylaluminum used is 1:1 to 50:1 - preferably 5:1 - and the reaction time, which can be monitored from the elimination of the alkane, is 1 to 200 hours - preferably 10 to 40 hours.
Of the aluminum salts containing water of crystalliza-tion, those are particularly used which have a high content of water of crystallization. Aluminum sulfate hydrate, in particular the compounds A1z ( S04 ) ~ .16H20 and Alz ( S04 ) 3.18Hz0 having the particularly high water of crystallization content of 16 and 18 moles of Hz0/mole of A12(S04)3 respectively, is particularly preferred.
A further variant for the preparation of aluminoxane is to dissolve trialkylaluminum, preferably tri.methylalumi-num, in the suspending agent initially introduced into the polymerization reactor and then to react the aluminum compound with water.
Besides the above-outlined proceesses for the preparation of aluminoxanes, there are otheris which can be used.
Irrespective of the manner of preparation, all alumin-oxane solutions have in common a varying content of unreacted trialkylaluminum, which is in free farm or in the form of an adduct. This content has an effect, as yet not explained accurately, on the catalytic effectiveness, which varies depending on the metallocene compound employed.
It is possible to pre-activate the metallocene using an aluminoxane of the formula II and/or III before using the polymerization reaction. This considerably increases the polymerization activity and improves the grain morpho-logy.
The preactivation of the transition-metal compound is carried out in solution. It is preferred here to dissolve the metallocene in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferably used.
The concentration of the aluminoxane 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 relative to the total solution. The metallocene can be employed in the same concentration, but it is preferably employed in an amount of from 10'4 - 1 mole per mole of aluminoxane. The pre-activation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. The pre-activation is carried out at a temperature of from -78°C to 100°C, preferably 0 to 70°C.
A significantly longer preactivation is possible, but normally has neither an activity-increasing nor activity reducing effect, but may be entirely appropriate fox storage purposes.
The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps,. at a temperature of from -60 to 200 °C, preferably -30 to 120 °C, in particular 50 to 90°C.
The overall pressure in the polymerization system is 0.5 to 200 bar. The polymerization is preferably carried out in the industrially particularly interesting pressure range of from 5 to 60 bar. The metallocene compound is used here in a concentration, relative to the transition metal, of from 10'3 to 10'a, preferably 10'4 to 10'' mole of transition metal per dm~ of solvent or per dm3 of reactor volume. The aluminoxane is used in a concentra-tion of from 10-5 to 10'1 mole, preferably 10'5 to 10-2 mole per dm3 of solvent or per dm3 of reactor volume. In 'L .~ ~ i principle, however, higher concentrations are also possible.
If the polymerization is carried out as a suspension or solution polymerization, a solvent which is inert towards Ziegler catalysts is used, i.e. an aliphatic or aromatic hydrocarbon. Aliphatic hydrocarbons are preferred, such as, for example, butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane or petroleum or hydrogenated diesel oil fractions.
Besides homopolymerization of ethylene, the catalyst systems according to the invention are employed for the copolymerization of ethylene with a 1-olefin having 3 to carbon atoms. Examples of such 1-olefins are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
15 The molecular weight of the polymer can be :regulated in a known manner, preferably using hydrogen.
The polymerization can have any desired duration, since the catalyst system to be used according to the invention only exhibits a slight time-depE:ndent decrease in poly 20 merization activity.
Depending on the structure of the complex, the use of these complexes gives, with high activities, polyethylene and ethylene-1-olefin copolymers having a narrow molecular-weight distribution (polydispersity) in a broad molecular-weight range, in particular products having high, molecular weights which are suitable for processing by injection molding and extrusion and in particular have high stretch-ing capacity of the polymer melt, and permits the produc-tion of very varied grain morphologies of the product, such as high and low bulk densities, extremely small and extremely large mean grain diameters and various grain shapes. The variety of grain morphologies which can be achieved opens up various possibilities for the use of such polyethylene powders in sintering processes.
The examples below are intended to illustrate the inven-tion.
The abbreviations have the following meaningse VN - viscosity number in cm3/g, l~t~" = weight average molecular weight in glmol, M",/M=, = molecular weight distribution determined by gel permeation chromatography (GFC), d5o = mean grain diameter in gym.
The pressure data in the examples are in bar of super-atmospheric pressure.
The densities of the copolymers have been determined in accordance with DIN 53479, method A.
All the operations below were carried out under a protec-~tive gas using absolute solvents.
Example 1:
Preparation of dimethylsilylbis(1-indenyl) 80 cm3 (0.20 mol) of a 2.5 molar solution of n-butyl-lithium in hexane were added with ace cooling to a solu-tion of 30 g (0.23 mol) of indene (technical grade, -91~) which has been filtered through aaluminum oxide. The batch was stirred for a further 15 minutes at room temperature, and the orange solution was added via a hollow needle over the course of 2 hours to a solution of 13.0 g (0.10 mol) of dimethyldichlorosilane (99~) in 30 cm3 of diethyl ether. The orange suspension was stirred over-night and washed by shaking three times with 100-150 cm3 of water. The yellow organic phase was dried twice over sodium sulfate and evaporated in the reaction evaporator.
The orange oil which remained was kept at 40°C for 4 to 5 hours in an oil-pump vacuum and freed from excess indene, during which a white precipitate deposited.
Addition of 40 cm3 of methanol and crystallization at -35°C gave a total of 20.4 g (7i~) of the compound dimethylsilylbis(1-indenyl) as a white to beige powder (2 diastereomers). M.p. 79-81°C.
Example 2:
Preparation of rac-di.methylsilylbis(1-indenyl)zirconium dichloride (metallocene A) . 5 cm3 ( 38 . 7 mmol ) of a 2 . 5 molar hexane solution of butyllithium were added slowly at room temperature to a solution of 5.6 g (19.4 mmol) of dimethylsilylbis(1-indenyl) in 40 cm3 of THF. 1 hour after completion of the 10 addition, the deep red solution was added dropwise over the course of 4-6 hours to a suspension of 7.3 g (19.4 mmol) of ZrCl~,.2THF in 60 cm3 of THF. After the mixture had been stirred for 2 hours, the orange precipi-tate was filtered off with suction via a glass frit and 15 recrystallized from CHZCIz, to give 1.0 g (11~) of the metallocene A in the form of orange crystals, which gradually decompose from 200°C.
Correct alementa~cy analyses. The E1 mass spectrum exhibi-ted M+ - 448. 1H NMR spectrum ((:DC13) : 7.04-7.60 (m, 8, arom. H), 6.90 (dd, 2, ,B-Ind H), 6.08 (d, 2, a-Ind H), 1.12 (s, 6, SiCH3).
Example 3:
Preparation of rac-diphenylsilylbis(1-indenyl)zirconium dichloride (metallocene B) A solution of 20 g (48.5 mmol) of (C6H5)2Si(Ind)2, prepared from (C~HS)2SiC12 and indenyllithium analogously to Example 1, in 200 cm3 of diethyl ether was reacted at 0°C with 40 cm3 (100 mmol) of butyllithium (2.5 molar in hexane).
After the mixture had been stirred at room temperature for 2 hours, the solvent was stripped off, and the residue was stirred with 100 cm3 of hexane and filtered off. The dilithio salt was dried in an oil-pump vacuum and added to a suspension of 11.3 g (48.5 mmol) of ZrCl4 in 150 cm3 of CHZC12 at -78°C. The mixture was stirred ~~~ =t~'~ ~ ~' .a L. .~ ~ ~
overnight and allowed to warm to room temperature. The red solution was concentrated, and the precipitate which deposited was filtered off via a frit. Extraction with toluene gave 2.0 g (7~) of metallocene B as an orange powder. Correct elementary analyses. 1H NMR spectrum (CDC13): 6.8-8.2 (m, 18, arom. H), 7.03 (dd, 2, p-Ind H), 6.30 (d, 2, «-Ind H).
Example 4:
Preparation of rac-dimethylsilylbis(1-(3-methylindenyl))-zirconium dichloride (metallocene G) A solution of 4.89 g (15.5 mmol) of (CH3)2Si(Melnd)2, prepared analogously to Example 1 from (CH3)ZSiClz and 3-methylindenyllithium, was reacted with 12.5 cm3 (30.5 mmol) of butyllithium and 5.84 g (15.5 mmol) df ZrC14.2THF analogously to Example 2. After the solvent had been stripped off, the residue was extracted with tolu-ene. The precipitate which deposited from toluene on concentration and cooling was rec:rystallized from CHC13, to give 800 mg (10~) of metallocene G in the form of orange-red crystals . Correct elementary analyses . 'H NM~t spectrum (CDC13): 7.0-7.5 (m, 8, arom. H), 5.71 (s, 2, «-Tnd H), 2.30 (s, 6, Ind CH3), 1.07 (s, 6, SiCH3).
Example 5:
Preparation of di:unethylsilylbis(1-(3-trimethylsilyl)-cyclopentadienyl)zircon3um dichloride (metallocene ~) A solution of 3.9 g ( 11.7 mmol) of (CH3)aSi[ (CH3)3SiCp]2, prepared from Liz [ ( CH3 ) ZSi ( Cp ) a 1 and ( CH3 ) 3SiCl, was reacted analogously to Example 2 with: 9.4 cm3 (23.4 mmol) of butyl-lithium and 4.4 g (11.7 mmol) of ZrC14.2THF. After the solvent had been stripped off, the residue was extracted with diethyl ether. The residue remaining after the diethyl ether had been stripped off was recrystallized from CHC13, to give 0.8 g (14~) of the complex as beige crystals . Correct elementary analyses . 1H NMR spectrum (GDC13): 6.95 (dd, 2, CpH), 6.12 (t, 2, CpH), 5.96 (t, 2, CpH), 0.72 (s, 6, Si(CH3)z), 0.25 (s, 9, Si(CH3)~). The NMR
spectrum showed that metallocene K was in the form of an isomer mixture {43~ of the rac-isomer, 57$ of the meso-isomer).
Example 6:
Preparation of isopropyl(1-indenyl)cyclopentadienylzir-conium dichloride (metallocene P) 19 cm3 (47.3 mmol) of butyllithium (2.5 molar in hexane) were added at room temperature to a solution of 6.0 g (47 mmol) of indene (91~) in 100 cm3 of diethyl ether.
After 1 hour, this solution was added to a solution of 6,6-dimethylfulvene in 100 cm3 of diethyl ether at -78°C.
After the mixture had been stirred at room temperature for 16 hours, the orange solution was diluted with 400 cm3 of diethyl ether, and 100 cm3 of water were added. The yellow organic phase was then washed twice with water, dried over NaZS04 and evaporated. The brown oii remaining was chromatographed on 400 g o:E silica gel 60. Using hexane + 7~ of methylene chlorid~, a 'total of 7.2 g (68~) of the compound isopropyl(1-inden;yl)cyclopentadienyl were eluted as a yellow oil (2 isomers). 28 cm3 (70 mmol) of buty:Llithium (2.5 molar in hexane) were added at 0°C to a solution of 7.1 g (32 mmol) of this compound in 100 cma of diethyl ether. After the mixture had been stirred at room temperature for 2 hours, the yellow precipitate was filtered off via a glass frit and washed with hexane/di-ethyl ether (1:1). After the precipitate had been dried in an oil-pump vacuum the pale yellow powder was added at -78°C to a suspension of 7.5 g (32 mmol) of ZrCl4 in 100 cm3 of methylene chloride. The mixture was slowly warmed to room temperature, stirred at room temperature for 30 minutes and filtered via a glass frit, and the solid was washed several times with methylene chloride.
The yellow filtrate was concentrated until crystalliza-tion occurred. At -35°C, a total of 2.4 g {19$) of the complex rac- ( ( CH3 ) ZC ( Tnd) Cp] ZrCl2 crystallized in the form of yellow-orange crystals . Correct elemewtazy analyses .
- 16 - ~r ~~
x zy 1H I~MR spectrum (CDC13)e 6.90-7.75 (m, 4, arom. H), 6.85 (dd, l, ~9-Ind-H), 6.52 (m, 2, Cp-H), 6.12 (d, 1, a-Ind-H), 5.82, 5.70 (2 x q, 2 x 1, Cp-H), 2.20; 1.95 (2 x s, 2 x 3 , CH3 ) .
Example 7:
Preparation of dipheny3~methylene(9-fluorenyl~lcyclopenta-dienylzirconium dichloride (metallocene Q~
12.3 cm3 (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium were slowly added at room temperature to ZO a solution of 5.10 g (30.7 mmol) of fluorene in 60 em3 of THF. After 40 minutes, 7.07 g (30.7 mmol) of diphenylful-vene were added to the orange solution, and the mixture was stirred overnight. 60 cm3 of water were added to the dark red solution, whereupon the solution became yellow, and the solution was extracted using ether. The ether phase, dried over MgS04, was concentrated and left to crystallize at -35°C, to give 5.1 g (42~) o:E 1,1-cyclo-pentadienyl(9-fluorenyl)diphenylmethane as a beige powder.
2.0 g (5.0 mmol) of the compound were dissolved in 20 cm3 of THF, and 6.4 cm3 (10 mmol) of a 1.6 molar solution of butyllithium in hexane were added at 0°C. After the mix-ture had been stirred at room temperature fox 15 minutes, the solvent was stripped off, and the red residue was dried in an oi.l-pump vacuum and washed several times with hexane. After the residue had been dried in an oil-pump vacuum, the red powder was added at -78°C to a suspension of 1.16 g (5.0 mmol) of ZrCl4. The batch was slowly warmed and stirred for a further 2 hours at room temperature.
The pink suspension was filtered via a G3 frit. The pink residue was washed with 20 cm3 Of CH2C12, dried in an oil-pump vacuum and extracted with 120 cm3 of toluene. Strip-ping off of the solvent and drying in an oil-pump vacuum gave 0.55 g of the zirconium complex (metallocene Q) in the form of a pink crystal powder.
~~~~~~r~.
_ 17 _ The orange-red filtrate of the reaction batch was eva-porated and left to crystallize at -35°C. A fuxther 0.34 g of the complex crystallizes from CHZC12. Total yield 1. 0 g ( 36~ ) . Correct elementary analyses . The mass spectrum exhibited M+ - 556. ~H NMR spectrum (100 MHz, CDC13) : 6.90-8.25 (m, 16, Flu-H, Ph-H), 6.40 (m, 2, Ph-H), 6.37 (t, 2, Cp-H), 5.80 (t, 2, Cp-H).
Examples 8-18:
The metallocenes C, D, E, F, H, I, >;, ~!, N, O and R of Table 2 were prepared analogously to Examples 1 and 2.
The di.methylchlorosilane in Example 1 was replaced here by appropriate other dihalogen compounds, which are shown in Table 1. In the case of complexes substituted on the 5-membered ring (metallocenes N and O), an i.ndene cor respondingly substituted on the 5-membered ring was employed (analogously to Example 4). zn the case of the hafnium complex metallocene R, ZrCl4 in Example 2 was replaced by HfClh.
Table 1 Example Metallocene Dihalocxe:n compound 8 C phenylmethyldichlorosilane 9 D phenylvi;nyldichlorosilane 10 E dimethyldichlorogermanium 11 F cyclotrimethylenedichlorosilane 12 H 1,1,2,2-tetramethyl-1,2-dichlorodisilane 13 I 1,2-bis(chlorodimethylsilyl)-ethane 24 L 1,2-dibromoethane 15 ri 1,3-dibromopropane 16 N 1,2-dibromoethane 17 O 1,2-dibromoethane 18 R 1,1,2,2-tetramethyl-1,2-dichlorosilane ~~v:
Example 19:
Preparation of phenylmethylmethylene(9-fluorenyl)cyclo-pentadienylhafnium dichloride (~aetallocene T) The metallocene T was prepared analogously to Example 7.
However, the diphenylfulvene and ZrCl4 in Example 7 were replaced by phenylmethylfulvene and HfCla.
Example 20:
dm3 of a petroleum ether (boiling range 100-120°C) were introduced at 20°C into a dry 16 dm3 reactor which had 10 been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by infecting 2 bar of ethylene and releasing the ethylene, and repeating this operation ~ times. 1 bar of hydrogen was then injected, and 30 cm3 of a toluene solution of methylaluminoxane (10.5$ by weight of methylaluminoxane, molecular weight 750 g/mol according to cryoscopic determination). The reactor contents were heated to 60°C over the course of 15 minutes with stirring. The overal:L pressure was then increased to 7 bar by introducing ethylene with stirring 2 0 at 250 rpm. At the same time, 3.1 mg of metallocene A were dissolved in 20 cm3 of a toluene solution of methylalumin-oxane (concentration and quality as above) and pre-activated by being left to stand for 15 minutes. The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 65°C
and then kept at this temperature for 1 hour by means of suitable cooling. The overall pressure was kept at 7 bar during this time by corresponding supply of ethylene.
160 g of polyethylene were obtained.
The following values were determined on the product:
VN = 152 cm3/g, bulk density: 320 g/dm3 Examples 21-42:
The procedure was in each case analogous to Example 20, but the following parameters were varied:
- metallocene type _ lg _ - metallocene quantity (mg) - methylaluminoxane solution type {content of methyl aluminoxane in ~ by weight, molecular weight M of the methylaluminoxane in g/mol according to cryo scopic determination) - amount of methylaluminoxane solution (cm3) introduced into the reactor - amount of hydrogen employed (HZ in bar, no hydrogen was employed in numerous experiments) - overall pressure P (bar) - polymerization time t (min) - polymerization temperature T (°C) The polymerization parameters which were varied are shown in Table 3, and the polymerization results are shown in Table 4.
Example 43s 10 dm3 of petroleum ether (boiling range 100--120°C) were introduced at 20°C into a dry 16 dm3 reactor which had been flushed with nitrogen. The c~as space of the reactor was then flushed free from nitrogen by injecting 2 bar of ethylene and releasing the ethylene, and repeating this operation 4 times . 200 cm3 of 1.-hexane and 30 cm3 of a toluene solution of methylaluminoxane { 10. 6~ by weight of methylaluminoxane, molecular weight 900 g/mol according to cryoscopic determination) were then added. The reactor was then heated to 60°C over the course of 15 minutes with stirring. The overall pressure was then increased to 5 bar by introducing ethylene with stirring at 250 rpm.
At the same tame, 1.3 mg ~f me~tallocene L were dissolved in 20 cm3 of a toluene solution of methylaluminoxane (con-centration and quality as above) and preactivated by being left to stand for 15 minutes . The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 80°C and then kept at this temperature for 45 minutes by suitable cooling. The overall pressure was kept at 5 bar during this time by appropriate supply of ethylene.
380 g of ethylene-1-hexene copolymer were obtained. The following values were determined on 'the products VN = 182 cm3/g density: 0.934 g/cm3.
Example 44:
dm3 of petroleum ether (boiling range 100-120°C) were introduced at 20 °C into a dry 16 dm3 reactor which had been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by injecting 2 bar of 10 ethylene and releasing the ethylene, and repeating this operation 4 times. 400 cm3 of 1-hexane and 30 cm3 of a toluene solution of methylaluminoxane (10.6 by weight of methylaluminoxane, molecular weight 900 g/mol according to cryoscopic determination) were then added. The reactor was then heated to 60°C over the course of 15 minutes with stirring. The overall pressure was then increased to 5 bar by introducing ethylene with stirring at 250 rpm.
At the same time, 1.3 mg of metallocene B were dissolved in cm3 of a toluene solution of methylaluminoxane (con 20 centration and quality as above) and preactivated by being left to stand for 15 minutes. The solution was then introduced into the reactor. Thin polymerization system was warmed to a temperature of 70°C and then kept at this temperature for 45 minutes by suitable cooling. The overall pressure was kept at 5 bar during this time by appropriate supply of ethylene.
520 g of ethylene-1-hexene copolymer were obtained. The following values were determined on the product:
VN = 168 cm3/g density: 0.924 g/cm3.
Example 45:
200 g of sodium chloride were introduced as a stirring aid in the gas phase at 20°C and under atmospheric pressure into a dry 1.5 dm3 reactor equipped with paddle stirrer which had been flushed with nitrogen. 5 bar of ethylene were then injected, and the stirrer was set at _ 21 _ 600 rpm. 5 cm3 of a toluene solution of methylaluminoxane (29.3 by weight of methylaluminoxane having a molecular weight of 1100 g/mol according to cryoscopic determina-tion) were then injected into the reactor by means of a spray nozzle, and the contents were stirred for 15 minutes.
At the same time, 1.1 mg of metallocene B were dissolved in 3 cm3 of a toluene solution of methylaluminoxane (con centration and quality as above) and preactivated by being left to stand for 15 minutes . This solution was then likewise injected into the reactor by means of a spray nozzle, and the temperature of the system was increased to 80°C. After a polymerization time of 20 minutes, the reactor was decompressed, the contents were removed, and the polymer formed was isolated by dissolv-ing the sodium chloride in water, and filtering off and drying the product.
14.5 g of polyethylene having VN - 240 cm3/g were obtained.
2 0 Example: 4 6 The procedure was as in Exampler 45, but the 1.1 mg of metallocene B were replaced by 0.9 mg of metallocene E.
10.4 g of polyethylene having a viscosity numbex VN = 230 cm3/g ware obtained.
Table 2 I~ietallocene abbreviation rac-Dimethylsilylbis(1-indenyl)zirconium dichloride rac-Diphenylsilylbis(1-indenyl)zirconium dichloride rac-Phenylmethylsilylbis(1-indenyl)zirconium dichloride G
rac-Phenylvinylsilylbis(1-indenyl)zirconium dichloride D
rac-Dimethylgermylbis(1-indenyl)zirconium dichloride E
1-Silacyclobutylbis(1'-indenyl)zirconium dichloride (isomer mixture: 57~ of rac-isomer, 43~ of meso-isomer) F
rac-Di.methylsilylbis(I-(3-methylindenyl))-zirconium dichloride G
rac-1,1,2,2-Tetramethyldisilaethylenebis-(1'-indenyl)zirconium dichloride H
rac-1,1,4,4-Tetramethyl-1,4 -disi:labutylenebis-(1'-indenyl)zirconium dichloride T
Dimethylsilylbis(1-(3-trimethyls:Lly1)cyclo-pentadienyl)zirconium dichloride (isomer mix-ture: 43~ of rac-isomer, 57~ of meso-isomer) K
rac-Ethylenebis(1-indenyl)zircon:Lum dichloride h Propylenebis(1-indenyl)zirconium dichloride M
Ethylenebis(1-(3-trimethylsilylindenyl))zir-conium dichloride (isomer mixture: 78~ of rac-isomer, 22~ of meso-isomer) N
rac-Ethylenebis(1-(3-allyldimethylsilyl-indenyl))-zirconium dichloride 0 Isopropyl(1-indenyl)cyclopentadienylzirconiwm dichloride P
Diphenylmethylene(9-fluorenyl)cyclogentadienyl-zirconium dichloride Q
rac-1,1,2,2-Tetramethyldisilaethylenebis(1'-indenyl)hafnium dichloride R
Phenylmethylmethylene(9-fluorenyljcyclopenta-dienylhafnium dichloride T
a7 Table Example lietallocene 3~4A0 Ha P t T
solution TypeAmountContentMN Amount (bar)(bar)(min)('C) in (mg) (x (e~mol)raa~tor by Weight) icm ) 21 A 4.0 10.5 750 50 - 5 60 65 22 B 3.9 10.6 900 30 - 5 60 65 23 C 7.2 10.7 1200 30 - 5 60 65 24 D 12.2 10.6 900 30 - 5 60 65 25 E 8.0 10.6 900 30 - 5 60 65 26 F 5.9 10.6 900 30 - 5 60 65 27 G 2.5 10.5 750 30 - 5 60 65 28 G 1.3 10.5 750 50 - 5 60 65 29 G 1.2 10.6 900 30 2 5 60 75 30 H 1.4 9.9 1100 30 - 5 60 65 31 2 48.3 9.9 1100 30 - 5 60 65 32 K 5.3 9.7 1000 60 - 5 60 70 33 L 1.2 10.1 1300 40 - S 300 65 34 M 7.3 9.9 1100 30 - 6 60 65 35 M 4.3 10.1 1300 30 - 5 120 65 36 N 6.8 9.9 1100 30 - 6 65 65 37 N 3.9 10.1 1300 30 0.5 5.5 80 65 38 0 11.6 10.7 1200 30 - 5 60 65 39 P 30.5 10,6 900 30 - 5 60 65 40 Q 5.0 10.6 900 30 - 5 60 65 41 R 6.9 10.1 1300 30 - 5 60 65 42 T 21.6 10.7 1200 30 - 6 60 65 ~~~o~.'~':
Table Example PolymerYN Zip Pf~/P~,Bulk d~Q
yield density (Cm3~g)~g~m01) ~g~~3) t/~m) 21 300 323 n.m. n.m. 210 SA
22 140 361 n.m, n.m. 280 n.m.
23 65 268 n.m. n.m. 300 n.m.
24 90 319 n.m. n.m. 310 n.m.
25 290 366 n.m. n.m. 140 n.m.
26 140 392 n.m, n.m. 180 n.m.
27 450 323 190000 4.5 170 150 28 S00 313 n.m, n.m. 200 180 29 240 36 n.m, n.m. 400 n.m.
30 170 911 720000 3.5 210 3500 31 590 642 480000 3.7 60 n.m.
32 1450 162 n.m. n.m. 300 50 33 590 198 n.m. n.m. 140 580 34 220 551 400000 LE.O 70 n.m.
35 310 624 n.m. n.m. 80 30 2 36 480 227 120000 2.3 120 n.m.
37 450 147 n.m. n.m. 300 n.m.
38 7S 230 n.m. n.m. 230 n.m.
39 1S0 78 n.m, n.m. 200 n.m.
40 100 746 n.m. n.m. 130 n.m.
41 35 1222 n.m. n.m. n.m, n.m.
42 60 711 n.m, n.m. n.m. n.m.
n.m. m not measured
M2 _ ~ _ M2 _ CR$ _ =BRs, =A1R6, -Ge-, -Sn-, -0-, -S-, =SO, =SO2, =IdRsr =C0, =PR6 or =P ( O ) R6, where R6, R' and R8 are identi-cal or different and are a hydrogen atom, a halogen atom, preferably chlorine, a C1-Clo-, preferably C1-C3-alkyl group, in particular a methyl group, a C1-Clo-fluoroalkyl group, preferably a CF3 group, a C6-Clo-fluoroaryl group, preferably a pentafluorophenyl group, a C6-Clo-, preferably C6-Ce-aryl group, a Cl_ Clo-. preferably Cl-C;,-alko~cy group, in particular a methoxy group, a GZ-Clo-, preferably CZ-C~-alkenyl group, a C~-C4o-, preferably C~-Clo-aryl alkyl group, a Ce-C4o-, preferably C8-C12-arylalkenyl group or a C~-C4o-, preferably C~-C12-alkylaryl group, or R6 and R' or R6 and Ro in each case, together with the atoms connecting them, form a ring, MZ is silicon, germanium or ti;n, preferably silicon or germanium, and p is the number 1, 2, 3, ~ or 5.
Particularly preferred metallocenes are:
rac-dimethylsilylbis(1-indenyl)zirconium dichloride, rac-diphenylsilyibis(1-indenyl)zirconium dichloride, 1-silacyclobutylbis(1'-indenyl)zirconium dichloride, rac-~dimethylsilylbis(1-(3-methylindenyl))ziroonium dichloride, rac-1,1,2,2-tetramethyldisilaethylenebis(1'-indenyl)zir-conium dichloride, dimethylsilylbis(1-(3-trimethylsilyl)cyclopentadienyl)-zirconitun dichloride, and diphenylmethylene(9-fluorenyl)cyclopentadienylzirconium dichloride.
The above-described metallocenes can be prepared by the general reaction scheme below:
_ H2R3+butylLi -~ HR~Li HR3-R5-R4H 2 b_utylLi~, HzR4+butylLi -~ HR'~Li ' LiR3-R5-R~Li tilltil i e' C1 ~ I / R1 ~~ p ~1 R5 M1 _ R1L ~. R5 ~ ~ R2~ R5 M1 a \Cl ~ 1 Cl -~ , ~ R2 R4 R~ . R~
(X = C1, Bx, I, O-tosyl) -- l _ or H2R3 + butylLi -~ HR3Li R6 R7 ~.-R4H
~ C / a, _HR3Li s R~R~C
R~' b, HAD \ R3H
2 butylLi a R
(R6R~C \ ]Lia R ~ ~ ~ ~,C1 R7/ \ ~ ~ C1 ~4 R
RlLi R ~ ~ s /R1 1~\ ~ ~ 1/ R1 C Ml R~Li~ ~C M~
R~ \ ~ ~ cl R~ \ ~ aRz Rg R4 The cocatalyst is an aluminoxane of the formula II
R~ Rg R~
\A1 - 0 ,~A1 - O A1 ~ ( II ) R~/ ~ n ~R~
for the linear type and/or of the formula III
_8_ A1 - O (III) n+2 for the cyclic type. In these formulae, R9 is a C1-Cs-alkyl group, preferably methyl, ethyl or isobutyl, butyl or neopentyl, or phenyl or benzyl. Methyl is particularly preferred. n is an integer from 2 to 50, preferably 5 to 40. However, the exact structure of the aluminoxane is not known.
The aluminoxane can be prepared in various ways.
One possibility is the careful addition of water to a dilute solution of a trialkylaluminum by introducing the solution of the trialkylaluminum, preferably trimethyl-aluminum, and the water in each case in small portions into an initially introduced larger amount of an inert solvent and between each portion awaiting the end of the evolution of gas.
In anothex process, finely powdered copper sulfate pentahydrate is slurried in toluene, and, in a glass flask under an inert gas at about -20°C, sufficient trialkylaluminum is added so that about 1 mole of CuS0,,.5H20 is available for each 4 A1 atoms. lifter slow hydrolysis with elimination of alkane, the reaction mixture is left at room temperature for 24 to 48 hours, cooling possibly being needed to ensure that the tempera-ture does not exceed 30°C. The aluminoxane dissolved in the toluene is subsequently filtered off from the copper sulfate, and the solution is evaporated in vacuo. It is assumed that the low-molecular-weight aluminoxanes condense in these preparation processes to form higher oligomers with elimination of trialkylaluminum.
Furthermore, aluminoxanes are obtained if trialkylalumi-num, preferably trimethylaluminum, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or g _ toluene, is reacted at a temperature of from -20 to 100°C
with aluminum salts, preferably aluminum sulfate, con-taining water of crystallization. In this case, the volume ratio between the solvent and the alkylaluminum used is 1:1 to 50:1 - preferably 5:1 - and the reaction time, which can be monitored from the elimination of the alkane, is 1 to 200 hours - preferably 10 to 40 hours.
Of the aluminum salts containing water of crystalliza-tion, those are particularly used which have a high content of water of crystallization. Aluminum sulfate hydrate, in particular the compounds A1z ( S04 ) ~ .16H20 and Alz ( S04 ) 3.18Hz0 having the particularly high water of crystallization content of 16 and 18 moles of Hz0/mole of A12(S04)3 respectively, is particularly preferred.
A further variant for the preparation of aluminoxane is to dissolve trialkylaluminum, preferably tri.methylalumi-num, in the suspending agent initially introduced into the polymerization reactor and then to react the aluminum compound with water.
Besides the above-outlined proceesses for the preparation of aluminoxanes, there are otheris which can be used.
Irrespective of the manner of preparation, all alumin-oxane solutions have in common a varying content of unreacted trialkylaluminum, which is in free farm or in the form of an adduct. This content has an effect, as yet not explained accurately, on the catalytic effectiveness, which varies depending on the metallocene compound employed.
It is possible to pre-activate the metallocene using an aluminoxane of the formula II and/or III before using the polymerization reaction. This considerably increases the polymerization activity and improves the grain morpho-logy.
The preactivation of the transition-metal compound is carried out in solution. It is preferred here to dissolve the metallocene in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferably used.
The concentration of the aluminoxane 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 relative to the total solution. The metallocene can be employed in the same concentration, but it is preferably employed in an amount of from 10'4 - 1 mole per mole of aluminoxane. The pre-activation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. The pre-activation is carried out at a temperature of from -78°C to 100°C, preferably 0 to 70°C.
A significantly longer preactivation is possible, but normally has neither an activity-increasing nor activity reducing effect, but may be entirely appropriate fox storage purposes.
The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps,. at a temperature of from -60 to 200 °C, preferably -30 to 120 °C, in particular 50 to 90°C.
The overall pressure in the polymerization system is 0.5 to 200 bar. The polymerization is preferably carried out in the industrially particularly interesting pressure range of from 5 to 60 bar. The metallocene compound is used here in a concentration, relative to the transition metal, of from 10'3 to 10'a, preferably 10'4 to 10'' mole of transition metal per dm~ of solvent or per dm3 of reactor volume. The aluminoxane is used in a concentra-tion of from 10-5 to 10'1 mole, preferably 10'5 to 10-2 mole per dm3 of solvent or per dm3 of reactor volume. In 'L .~ ~ i principle, however, higher concentrations are also possible.
If the polymerization is carried out as a suspension or solution polymerization, a solvent which is inert towards Ziegler catalysts is used, i.e. an aliphatic or aromatic hydrocarbon. Aliphatic hydrocarbons are preferred, such as, for example, butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane or petroleum or hydrogenated diesel oil fractions.
Besides homopolymerization of ethylene, the catalyst systems according to the invention are employed for the copolymerization of ethylene with a 1-olefin having 3 to carbon atoms. Examples of such 1-olefins are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
15 The molecular weight of the polymer can be :regulated in a known manner, preferably using hydrogen.
The polymerization can have any desired duration, since the catalyst system to be used according to the invention only exhibits a slight time-depE:ndent decrease in poly 20 merization activity.
Depending on the structure of the complex, the use of these complexes gives, with high activities, polyethylene and ethylene-1-olefin copolymers having a narrow molecular-weight distribution (polydispersity) in a broad molecular-weight range, in particular products having high, molecular weights which are suitable for processing by injection molding and extrusion and in particular have high stretch-ing capacity of the polymer melt, and permits the produc-tion of very varied grain morphologies of the product, such as high and low bulk densities, extremely small and extremely large mean grain diameters and various grain shapes. The variety of grain morphologies which can be achieved opens up various possibilities for the use of such polyethylene powders in sintering processes.
The examples below are intended to illustrate the inven-tion.
The abbreviations have the following meaningse VN - viscosity number in cm3/g, l~t~" = weight average molecular weight in glmol, M",/M=, = molecular weight distribution determined by gel permeation chromatography (GFC), d5o = mean grain diameter in gym.
The pressure data in the examples are in bar of super-atmospheric pressure.
The densities of the copolymers have been determined in accordance with DIN 53479, method A.
All the operations below were carried out under a protec-~tive gas using absolute solvents.
Example 1:
Preparation of dimethylsilylbis(1-indenyl) 80 cm3 (0.20 mol) of a 2.5 molar solution of n-butyl-lithium in hexane were added with ace cooling to a solu-tion of 30 g (0.23 mol) of indene (technical grade, -91~) which has been filtered through aaluminum oxide. The batch was stirred for a further 15 minutes at room temperature, and the orange solution was added via a hollow needle over the course of 2 hours to a solution of 13.0 g (0.10 mol) of dimethyldichlorosilane (99~) in 30 cm3 of diethyl ether. The orange suspension was stirred over-night and washed by shaking three times with 100-150 cm3 of water. The yellow organic phase was dried twice over sodium sulfate and evaporated in the reaction evaporator.
The orange oil which remained was kept at 40°C for 4 to 5 hours in an oil-pump vacuum and freed from excess indene, during which a white precipitate deposited.
Addition of 40 cm3 of methanol and crystallization at -35°C gave a total of 20.4 g (7i~) of the compound dimethylsilylbis(1-indenyl) as a white to beige powder (2 diastereomers). M.p. 79-81°C.
Example 2:
Preparation of rac-di.methylsilylbis(1-indenyl)zirconium dichloride (metallocene A) . 5 cm3 ( 38 . 7 mmol ) of a 2 . 5 molar hexane solution of butyllithium were added slowly at room temperature to a solution of 5.6 g (19.4 mmol) of dimethylsilylbis(1-indenyl) in 40 cm3 of THF. 1 hour after completion of the 10 addition, the deep red solution was added dropwise over the course of 4-6 hours to a suspension of 7.3 g (19.4 mmol) of ZrCl~,.2THF in 60 cm3 of THF. After the mixture had been stirred for 2 hours, the orange precipi-tate was filtered off with suction via a glass frit and 15 recrystallized from CHZCIz, to give 1.0 g (11~) of the metallocene A in the form of orange crystals, which gradually decompose from 200°C.
Correct alementa~cy analyses. The E1 mass spectrum exhibi-ted M+ - 448. 1H NMR spectrum ((:DC13) : 7.04-7.60 (m, 8, arom. H), 6.90 (dd, 2, ,B-Ind H), 6.08 (d, 2, a-Ind H), 1.12 (s, 6, SiCH3).
Example 3:
Preparation of rac-diphenylsilylbis(1-indenyl)zirconium dichloride (metallocene B) A solution of 20 g (48.5 mmol) of (C6H5)2Si(Ind)2, prepared from (C~HS)2SiC12 and indenyllithium analogously to Example 1, in 200 cm3 of diethyl ether was reacted at 0°C with 40 cm3 (100 mmol) of butyllithium (2.5 molar in hexane).
After the mixture had been stirred at room temperature for 2 hours, the solvent was stripped off, and the residue was stirred with 100 cm3 of hexane and filtered off. The dilithio salt was dried in an oil-pump vacuum and added to a suspension of 11.3 g (48.5 mmol) of ZrCl4 in 150 cm3 of CHZC12 at -78°C. The mixture was stirred ~~~ =t~'~ ~ ~' .a L. .~ ~ ~
overnight and allowed to warm to room temperature. The red solution was concentrated, and the precipitate which deposited was filtered off via a frit. Extraction with toluene gave 2.0 g (7~) of metallocene B as an orange powder. Correct elementary analyses. 1H NMR spectrum (CDC13): 6.8-8.2 (m, 18, arom. H), 7.03 (dd, 2, p-Ind H), 6.30 (d, 2, «-Ind H).
Example 4:
Preparation of rac-dimethylsilylbis(1-(3-methylindenyl))-zirconium dichloride (metallocene G) A solution of 4.89 g (15.5 mmol) of (CH3)2Si(Melnd)2, prepared analogously to Example 1 from (CH3)ZSiClz and 3-methylindenyllithium, was reacted with 12.5 cm3 (30.5 mmol) of butyllithium and 5.84 g (15.5 mmol) df ZrC14.2THF analogously to Example 2. After the solvent had been stripped off, the residue was extracted with tolu-ene. The precipitate which deposited from toluene on concentration and cooling was rec:rystallized from CHC13, to give 800 mg (10~) of metallocene G in the form of orange-red crystals . Correct elementary analyses . 'H NM~t spectrum (CDC13): 7.0-7.5 (m, 8, arom. H), 5.71 (s, 2, «-Tnd H), 2.30 (s, 6, Ind CH3), 1.07 (s, 6, SiCH3).
Example 5:
Preparation of di:unethylsilylbis(1-(3-trimethylsilyl)-cyclopentadienyl)zircon3um dichloride (metallocene ~) A solution of 3.9 g ( 11.7 mmol) of (CH3)aSi[ (CH3)3SiCp]2, prepared from Liz [ ( CH3 ) ZSi ( Cp ) a 1 and ( CH3 ) 3SiCl, was reacted analogously to Example 2 with: 9.4 cm3 (23.4 mmol) of butyl-lithium and 4.4 g (11.7 mmol) of ZrC14.2THF. After the solvent had been stripped off, the residue was extracted with diethyl ether. The residue remaining after the diethyl ether had been stripped off was recrystallized from CHC13, to give 0.8 g (14~) of the complex as beige crystals . Correct elementary analyses . 1H NMR spectrum (GDC13): 6.95 (dd, 2, CpH), 6.12 (t, 2, CpH), 5.96 (t, 2, CpH), 0.72 (s, 6, Si(CH3)z), 0.25 (s, 9, Si(CH3)~). The NMR
spectrum showed that metallocene K was in the form of an isomer mixture {43~ of the rac-isomer, 57$ of the meso-isomer).
Example 6:
Preparation of isopropyl(1-indenyl)cyclopentadienylzir-conium dichloride (metallocene P) 19 cm3 (47.3 mmol) of butyllithium (2.5 molar in hexane) were added at room temperature to a solution of 6.0 g (47 mmol) of indene (91~) in 100 cm3 of diethyl ether.
After 1 hour, this solution was added to a solution of 6,6-dimethylfulvene in 100 cm3 of diethyl ether at -78°C.
After the mixture had been stirred at room temperature for 16 hours, the orange solution was diluted with 400 cm3 of diethyl ether, and 100 cm3 of water were added. The yellow organic phase was then washed twice with water, dried over NaZS04 and evaporated. The brown oii remaining was chromatographed on 400 g o:E silica gel 60. Using hexane + 7~ of methylene chlorid~, a 'total of 7.2 g (68~) of the compound isopropyl(1-inden;yl)cyclopentadienyl were eluted as a yellow oil (2 isomers). 28 cm3 (70 mmol) of buty:Llithium (2.5 molar in hexane) were added at 0°C to a solution of 7.1 g (32 mmol) of this compound in 100 cma of diethyl ether. After the mixture had been stirred at room temperature for 2 hours, the yellow precipitate was filtered off via a glass frit and washed with hexane/di-ethyl ether (1:1). After the precipitate had been dried in an oil-pump vacuum the pale yellow powder was added at -78°C to a suspension of 7.5 g (32 mmol) of ZrCl4 in 100 cm3 of methylene chloride. The mixture was slowly warmed to room temperature, stirred at room temperature for 30 minutes and filtered via a glass frit, and the solid was washed several times with methylene chloride.
The yellow filtrate was concentrated until crystalliza-tion occurred. At -35°C, a total of 2.4 g {19$) of the complex rac- ( ( CH3 ) ZC ( Tnd) Cp] ZrCl2 crystallized in the form of yellow-orange crystals . Correct elemewtazy analyses .
- 16 - ~r ~~
x zy 1H I~MR spectrum (CDC13)e 6.90-7.75 (m, 4, arom. H), 6.85 (dd, l, ~9-Ind-H), 6.52 (m, 2, Cp-H), 6.12 (d, 1, a-Ind-H), 5.82, 5.70 (2 x q, 2 x 1, Cp-H), 2.20; 1.95 (2 x s, 2 x 3 , CH3 ) .
Example 7:
Preparation of dipheny3~methylene(9-fluorenyl~lcyclopenta-dienylzirconium dichloride (metallocene Q~
12.3 cm3 (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium were slowly added at room temperature to ZO a solution of 5.10 g (30.7 mmol) of fluorene in 60 em3 of THF. After 40 minutes, 7.07 g (30.7 mmol) of diphenylful-vene were added to the orange solution, and the mixture was stirred overnight. 60 cm3 of water were added to the dark red solution, whereupon the solution became yellow, and the solution was extracted using ether. The ether phase, dried over MgS04, was concentrated and left to crystallize at -35°C, to give 5.1 g (42~) o:E 1,1-cyclo-pentadienyl(9-fluorenyl)diphenylmethane as a beige powder.
2.0 g (5.0 mmol) of the compound were dissolved in 20 cm3 of THF, and 6.4 cm3 (10 mmol) of a 1.6 molar solution of butyllithium in hexane were added at 0°C. After the mix-ture had been stirred at room temperature fox 15 minutes, the solvent was stripped off, and the red residue was dried in an oi.l-pump vacuum and washed several times with hexane. After the residue had been dried in an oil-pump vacuum, the red powder was added at -78°C to a suspension of 1.16 g (5.0 mmol) of ZrCl4. The batch was slowly warmed and stirred for a further 2 hours at room temperature.
The pink suspension was filtered via a G3 frit. The pink residue was washed with 20 cm3 Of CH2C12, dried in an oil-pump vacuum and extracted with 120 cm3 of toluene. Strip-ping off of the solvent and drying in an oil-pump vacuum gave 0.55 g of the zirconium complex (metallocene Q) in the form of a pink crystal powder.
~~~~~~r~.
_ 17 _ The orange-red filtrate of the reaction batch was eva-porated and left to crystallize at -35°C. A fuxther 0.34 g of the complex crystallizes from CHZC12. Total yield 1. 0 g ( 36~ ) . Correct elementary analyses . The mass spectrum exhibited M+ - 556. ~H NMR spectrum (100 MHz, CDC13) : 6.90-8.25 (m, 16, Flu-H, Ph-H), 6.40 (m, 2, Ph-H), 6.37 (t, 2, Cp-H), 5.80 (t, 2, Cp-H).
Examples 8-18:
The metallocenes C, D, E, F, H, I, >;, ~!, N, O and R of Table 2 were prepared analogously to Examples 1 and 2.
The di.methylchlorosilane in Example 1 was replaced here by appropriate other dihalogen compounds, which are shown in Table 1. In the case of complexes substituted on the 5-membered ring (metallocenes N and O), an i.ndene cor respondingly substituted on the 5-membered ring was employed (analogously to Example 4). zn the case of the hafnium complex metallocene R, ZrCl4 in Example 2 was replaced by HfClh.
Table 1 Example Metallocene Dihalocxe:n compound 8 C phenylmethyldichlorosilane 9 D phenylvi;nyldichlorosilane 10 E dimethyldichlorogermanium 11 F cyclotrimethylenedichlorosilane 12 H 1,1,2,2-tetramethyl-1,2-dichlorodisilane 13 I 1,2-bis(chlorodimethylsilyl)-ethane 24 L 1,2-dibromoethane 15 ri 1,3-dibromopropane 16 N 1,2-dibromoethane 17 O 1,2-dibromoethane 18 R 1,1,2,2-tetramethyl-1,2-dichlorosilane ~~v:
Example 19:
Preparation of phenylmethylmethylene(9-fluorenyl)cyclo-pentadienylhafnium dichloride (~aetallocene T) The metallocene T was prepared analogously to Example 7.
However, the diphenylfulvene and ZrCl4 in Example 7 were replaced by phenylmethylfulvene and HfCla.
Example 20:
dm3 of a petroleum ether (boiling range 100-120°C) were introduced at 20°C into a dry 16 dm3 reactor which had 10 been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by infecting 2 bar of ethylene and releasing the ethylene, and repeating this operation ~ times. 1 bar of hydrogen was then injected, and 30 cm3 of a toluene solution of methylaluminoxane (10.5$ by weight of methylaluminoxane, molecular weight 750 g/mol according to cryoscopic determination). The reactor contents were heated to 60°C over the course of 15 minutes with stirring. The overal:L pressure was then increased to 7 bar by introducing ethylene with stirring 2 0 at 250 rpm. At the same time, 3.1 mg of metallocene A were dissolved in 20 cm3 of a toluene solution of methylalumin-oxane (concentration and quality as above) and pre-activated by being left to stand for 15 minutes. The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 65°C
and then kept at this temperature for 1 hour by means of suitable cooling. The overall pressure was kept at 7 bar during this time by corresponding supply of ethylene.
160 g of polyethylene were obtained.
The following values were determined on the product:
VN = 152 cm3/g, bulk density: 320 g/dm3 Examples 21-42:
The procedure was in each case analogous to Example 20, but the following parameters were varied:
- metallocene type _ lg _ - metallocene quantity (mg) - methylaluminoxane solution type {content of methyl aluminoxane in ~ by weight, molecular weight M of the methylaluminoxane in g/mol according to cryo scopic determination) - amount of methylaluminoxane solution (cm3) introduced into the reactor - amount of hydrogen employed (HZ in bar, no hydrogen was employed in numerous experiments) - overall pressure P (bar) - polymerization time t (min) - polymerization temperature T (°C) The polymerization parameters which were varied are shown in Table 3, and the polymerization results are shown in Table 4.
Example 43s 10 dm3 of petroleum ether (boiling range 100--120°C) were introduced at 20°C into a dry 16 dm3 reactor which had been flushed with nitrogen. The c~as space of the reactor was then flushed free from nitrogen by injecting 2 bar of ethylene and releasing the ethylene, and repeating this operation 4 times . 200 cm3 of 1.-hexane and 30 cm3 of a toluene solution of methylaluminoxane { 10. 6~ by weight of methylaluminoxane, molecular weight 900 g/mol according to cryoscopic determination) were then added. The reactor was then heated to 60°C over the course of 15 minutes with stirring. The overall pressure was then increased to 5 bar by introducing ethylene with stirring at 250 rpm.
At the same tame, 1.3 mg ~f me~tallocene L were dissolved in 20 cm3 of a toluene solution of methylaluminoxane (con-centration and quality as above) and preactivated by being left to stand for 15 minutes . The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 80°C and then kept at this temperature for 45 minutes by suitable cooling. The overall pressure was kept at 5 bar during this time by appropriate supply of ethylene.
380 g of ethylene-1-hexene copolymer were obtained. The following values were determined on 'the products VN = 182 cm3/g density: 0.934 g/cm3.
Example 44:
dm3 of petroleum ether (boiling range 100-120°C) were introduced at 20 °C into a dry 16 dm3 reactor which had been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by injecting 2 bar of 10 ethylene and releasing the ethylene, and repeating this operation 4 times. 400 cm3 of 1-hexane and 30 cm3 of a toluene solution of methylaluminoxane (10.6 by weight of methylaluminoxane, molecular weight 900 g/mol according to cryoscopic determination) were then added. The reactor was then heated to 60°C over the course of 15 minutes with stirring. The overall pressure was then increased to 5 bar by introducing ethylene with stirring at 250 rpm.
At the same time, 1.3 mg of metallocene B were dissolved in cm3 of a toluene solution of methylaluminoxane (con 20 centration and quality as above) and preactivated by being left to stand for 15 minutes. The solution was then introduced into the reactor. Thin polymerization system was warmed to a temperature of 70°C and then kept at this temperature for 45 minutes by suitable cooling. The overall pressure was kept at 5 bar during this time by appropriate supply of ethylene.
520 g of ethylene-1-hexene copolymer were obtained. The following values were determined on the product:
VN = 168 cm3/g density: 0.924 g/cm3.
Example 45:
200 g of sodium chloride were introduced as a stirring aid in the gas phase at 20°C and under atmospheric pressure into a dry 1.5 dm3 reactor equipped with paddle stirrer which had been flushed with nitrogen. 5 bar of ethylene were then injected, and the stirrer was set at _ 21 _ 600 rpm. 5 cm3 of a toluene solution of methylaluminoxane (29.3 by weight of methylaluminoxane having a molecular weight of 1100 g/mol according to cryoscopic determina-tion) were then injected into the reactor by means of a spray nozzle, and the contents were stirred for 15 minutes.
At the same time, 1.1 mg of metallocene B were dissolved in 3 cm3 of a toluene solution of methylaluminoxane (con centration and quality as above) and preactivated by being left to stand for 15 minutes . This solution was then likewise injected into the reactor by means of a spray nozzle, and the temperature of the system was increased to 80°C. After a polymerization time of 20 minutes, the reactor was decompressed, the contents were removed, and the polymer formed was isolated by dissolv-ing the sodium chloride in water, and filtering off and drying the product.
14.5 g of polyethylene having VN - 240 cm3/g were obtained.
2 0 Example: 4 6 The procedure was as in Exampler 45, but the 1.1 mg of metallocene B were replaced by 0.9 mg of metallocene E.
10.4 g of polyethylene having a viscosity numbex VN = 230 cm3/g ware obtained.
Table 2 I~ietallocene abbreviation rac-Dimethylsilylbis(1-indenyl)zirconium dichloride rac-Diphenylsilylbis(1-indenyl)zirconium dichloride rac-Phenylmethylsilylbis(1-indenyl)zirconium dichloride G
rac-Phenylvinylsilylbis(1-indenyl)zirconium dichloride D
rac-Dimethylgermylbis(1-indenyl)zirconium dichloride E
1-Silacyclobutylbis(1'-indenyl)zirconium dichloride (isomer mixture: 57~ of rac-isomer, 43~ of meso-isomer) F
rac-Di.methylsilylbis(I-(3-methylindenyl))-zirconium dichloride G
rac-1,1,2,2-Tetramethyldisilaethylenebis-(1'-indenyl)zirconium dichloride H
rac-1,1,4,4-Tetramethyl-1,4 -disi:labutylenebis-(1'-indenyl)zirconium dichloride T
Dimethylsilylbis(1-(3-trimethyls:Lly1)cyclo-pentadienyl)zirconium dichloride (isomer mix-ture: 43~ of rac-isomer, 57~ of meso-isomer) K
rac-Ethylenebis(1-indenyl)zircon:Lum dichloride h Propylenebis(1-indenyl)zirconium dichloride M
Ethylenebis(1-(3-trimethylsilylindenyl))zir-conium dichloride (isomer mixture: 78~ of rac-isomer, 22~ of meso-isomer) N
rac-Ethylenebis(1-(3-allyldimethylsilyl-indenyl))-zirconium dichloride 0 Isopropyl(1-indenyl)cyclopentadienylzirconiwm dichloride P
Diphenylmethylene(9-fluorenyl)cyclogentadienyl-zirconium dichloride Q
rac-1,1,2,2-Tetramethyldisilaethylenebis(1'-indenyl)hafnium dichloride R
Phenylmethylmethylene(9-fluorenyljcyclopenta-dienylhafnium dichloride T
a7 Table Example lietallocene 3~4A0 Ha P t T
solution TypeAmountContentMN Amount (bar)(bar)(min)('C) in (mg) (x (e~mol)raa~tor by Weight) icm ) 21 A 4.0 10.5 750 50 - 5 60 65 22 B 3.9 10.6 900 30 - 5 60 65 23 C 7.2 10.7 1200 30 - 5 60 65 24 D 12.2 10.6 900 30 - 5 60 65 25 E 8.0 10.6 900 30 - 5 60 65 26 F 5.9 10.6 900 30 - 5 60 65 27 G 2.5 10.5 750 30 - 5 60 65 28 G 1.3 10.5 750 50 - 5 60 65 29 G 1.2 10.6 900 30 2 5 60 75 30 H 1.4 9.9 1100 30 - 5 60 65 31 2 48.3 9.9 1100 30 - 5 60 65 32 K 5.3 9.7 1000 60 - 5 60 70 33 L 1.2 10.1 1300 40 - S 300 65 34 M 7.3 9.9 1100 30 - 6 60 65 35 M 4.3 10.1 1300 30 - 5 120 65 36 N 6.8 9.9 1100 30 - 6 65 65 37 N 3.9 10.1 1300 30 0.5 5.5 80 65 38 0 11.6 10.7 1200 30 - 5 60 65 39 P 30.5 10,6 900 30 - 5 60 65 40 Q 5.0 10.6 900 30 - 5 60 65 41 R 6.9 10.1 1300 30 - 5 60 65 42 T 21.6 10.7 1200 30 - 6 60 65 ~~~o~.'~':
Table Example PolymerYN Zip Pf~/P~,Bulk d~Q
yield density (Cm3~g)~g~m01) ~g~~3) t/~m) 21 300 323 n.m. n.m. 210 SA
22 140 361 n.m, n.m. 280 n.m.
23 65 268 n.m. n.m. 300 n.m.
24 90 319 n.m. n.m. 310 n.m.
25 290 366 n.m. n.m. 140 n.m.
26 140 392 n.m, n.m. 180 n.m.
27 450 323 190000 4.5 170 150 28 S00 313 n.m, n.m. 200 180 29 240 36 n.m, n.m. 400 n.m.
30 170 911 720000 3.5 210 3500 31 590 642 480000 3.7 60 n.m.
32 1450 162 n.m. n.m. 300 50 33 590 198 n.m. n.m. 140 580 34 220 551 400000 LE.O 70 n.m.
35 310 624 n.m. n.m. 80 30 2 36 480 227 120000 2.3 120 n.m.
37 450 147 n.m. n.m. 300 n.m.
38 7S 230 n.m. n.m. 230 n.m.
39 1S0 78 n.m, n.m. 200 n.m.
40 100 746 n.m. n.m. 130 n.m.
41 35 1222 n.m. n.m. n.m, n.m.
42 60 711 n.m, n.m. n.m. n.m.
n.m. m not measured
Claims (6)
1. A process for the preparation of ethylene polymers by polymerization of ethylene or copolymerization of ethylene with 1-olefins having 3 to 20 carbon atoms at a temperature of from -60 to 200°C and a pressure of from 0.5 to 200 bar in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a metallocene as the transition-metal component and an aluminoxane of the formula II
for the linear type and/or of the formulae III
for the cyclic type, where, in the formulae II and III, R9 is a C1-C8-alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition-metal component is a compound of the formula I
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1 and R2 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C4o-arylalkenyl group, R3 and R4 are identical or different and are indenyl, or fluorenyl, having additional substituents, which with the cental atom M1, is able to form a sandwich structure, R5 is =BR6, =A1R6, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR6, =CO, =PR6 or =P ( O ) R6, where R6, R7 and R8 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10 fluoroalkyl group, a C6-C10-fluoroaryl group, a C5-C10-aryl group, a C1-C10-alkoxy group, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R6 and R7 or R6 and R8, in each case with the atoms connecting them, form a ring, M2 is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or 5, or the transition-metal component is diphenylmethylene (9-fluorenyl) cyclopentadienyl-zirconium dichloride, phenylmethylmethylene (9-fluorenyl) cyclopentadienylhafnium dichloride, Rac-dimethylsilylbis (1-(3-methylindenyl)) zirconium dichloride.
for the linear type and/or of the formulae III
for the cyclic type, where, in the formulae II and III, R9 is a C1-C8-alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition-metal component is a compound of the formula I
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1 and R2 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C4o-arylalkenyl group, R3 and R4 are identical or different and are indenyl, or fluorenyl, having additional substituents, which with the cental atom M1, is able to form a sandwich structure, R5 is =BR6, =A1R6, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR6, =CO, =PR6 or =P ( O ) R6, where R6, R7 and R8 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10 fluoroalkyl group, a C6-C10-fluoroaryl group, a C5-C10-aryl group, a C1-C10-alkoxy group, a C2-C10 alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R6 and R7 or R6 and R8, in each case with the atoms connecting them, form a ring, M2 is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or 5, or the transition-metal component is diphenylmethylene (9-fluorenyl) cyclopentadienyl-zirconium dichloride, phenylmethylmethylene (9-fluorenyl) cyclopentadienylhafnium dichloride, Rac-dimethylsilylbis (1-(3-methylindenyl)) zirconium dichloride.
2. A metallocene of the formula I:
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1 and R2 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are identical or different and are indenyl, or fluorenyl, having additional substituents, which, with the central atom M1, is able to form a sandwich structure, R5 is = BR6, - A1R6, -Ge-, -Sn-, -O-, -S-, - SO, =
SO2, - NR6, - CO, - PR6 or = P (O) R6, where R6, R7 and R8 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group, or a C7-C40-alkylaryl group, or R6 and R7 or R6 and R8, in each case with the atoms connecting them, form a ring, M2 is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or 5.
in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum, R1 and R2 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are identical or different and are indenyl, or fluorenyl, having additional substituents, which, with the central atom M1, is able to form a sandwich structure, R5 is = BR6, - A1R6, -Ge-, -Sn-, -O-, -S-, - SO, =
SO2, - NR6, - CO, - PR6 or = P (O) R6, where R6, R7 and R8 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group, or a C7-C40-alkylaryl group, or R6 and R7 or R6 and R8, in each case with the atoms connecting them, form a ring, M2 is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or 5.
3. The metallocene as claimed in claim 2 wherein:
M1 is zirconium;
R1 and R2 are a hydrogen atom, C1-C3-alkyl, C1-C3-alkoxy, C6-C8-aryl, C6-C8-aryloxy, C2-C4-alkenyl, C7-C10-arylalkyl; C7-C12-alkylaryl, C8-C12-arylalkenyl or chlorine;
M2 is silicon or germanium; and p is the number 1, 2, 3, 4 or 5.
M1 is zirconium;
R1 and R2 are a hydrogen atom, C1-C3-alkyl, C1-C3-alkoxy, C6-C8-aryl, C6-C8-aryloxy, C2-C4-alkenyl, C7-C10-arylalkyl; C7-C12-alkylaryl, C8-C12-arylalkenyl or chlorine;
M2 is silicon or germanium; and p is the number 1, 2, 3, 4 or 5.
4. A metallocene as claimed in claim 2 which is diphenylmethylene (9-fluorenyl) cyclopentadienylzirconium dichloride, phenylmethylmethylene (9-fluorenyl) cyclopentadienylhafnium dichloride, rac-dimethylsilylbis (1-(3-methylindenyl))-zirconium dichloride.
5. A catalyst comprising:
(a) a metallocene as claimed in any one of claims 2-4; and (b) an aluminoxane.
(a) a metallocene as claimed in any one of claims 2-4; and (b) an aluminoxane.
6. The catalyst according to claim 5 wherein the aluminoxane is of the formula II
wherein:
R9 is a C1-C6 alkyl group or phenyl and n is an integer from 2 to 50.
wherein:
R9 is a C1-C6 alkyl group or phenyl and n is an integer from 2 to 50.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3916555A DE3916555A1 (en) | 1989-05-20 | 1989-05-20 | PROCESS FOR THE PRODUCTION OF ETHYLENE POLYMERS |
| DEP3916555.8 | 1989-05-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2017190A1 CA2017190A1 (en) | 1990-11-20 |
| CA2017190C true CA2017190C (en) | 2001-01-30 |
Family
ID=6381117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002017190A Expired - Lifetime CA2017190C (en) | 1989-05-20 | 1990-05-18 | Process for the preparation of ethylene polymers |
Country Status (7)
| Country | Link |
|---|---|
| EP (2) | EP0700937B1 (en) |
| JP (1) | JP2904301B2 (en) |
| AU (1) | AU630451B2 (en) |
| CA (1) | CA2017190C (en) |
| DE (3) | DE3916555A1 (en) |
| ES (2) | ES2116263T3 (en) |
| ZA (1) | ZA903831B (en) |
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| US10377886B2 (en) | 2015-03-31 | 2019-08-13 | Japan Polyethylene Corporation | Polyethylene for pipe and joint, and molded body thereof |
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-
1989
- 1989-05-20 DE DE3916555A patent/DE3916555A1/en not_active Withdrawn
-
1990
- 1990-05-16 EP EP95117503A patent/EP0700937B1/en not_active Expired - Lifetime
- 1990-05-16 EP EP90109207A patent/EP0399348B1/en not_active Expired - Lifetime
- 1990-05-16 DE DE59010821T patent/DE59010821D1/en not_active Expired - Lifetime
- 1990-05-16 ES ES90109207T patent/ES2116263T3/en not_active Expired - Lifetime
- 1990-05-16 DE DE59010898T patent/DE59010898D1/en not_active Expired - Lifetime
- 1990-05-16 ES ES95117503T patent/ES2144089T3/en not_active Expired - Lifetime
- 1990-05-18 CA CA002017190A patent/CA2017190C/en not_active Expired - Lifetime
- 1990-05-18 JP JP2127075A patent/JP2904301B2/en not_active Expired - Fee Related
- 1990-05-18 ZA ZA903831A patent/ZA903831B/en unknown
- 1990-05-23 AU AU55771/90A patent/AU630451B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10377886B2 (en) | 2015-03-31 | 2019-08-13 | Japan Polyethylene Corporation | Polyethylene for pipe and joint, and molded body thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0399348A3 (en) | 1992-08-12 |
| DE3916555A1 (en) | 1990-11-22 |
| EP0700937A3 (en) | 1997-02-19 |
| CA2017190A1 (en) | 1990-11-20 |
| ZA903831B (en) | 1991-02-27 |
| EP0399348A2 (en) | 1990-11-28 |
| EP0399348B1 (en) | 1998-05-20 |
| EP0700937B1 (en) | 2000-02-16 |
| JPH0321607A (en) | 1991-01-30 |
| JP2904301B2 (en) | 1999-06-14 |
| EP0700937A2 (en) | 1996-03-13 |
| ES2144089T3 (en) | 2000-06-01 |
| AU5577190A (en) | 1991-01-10 |
| AU630451B2 (en) | 1992-10-29 |
| ES2116263T3 (en) | 1998-07-16 |
| DE59010898D1 (en) | 2000-03-23 |
| DE59010821D1 (en) | 1998-06-25 |
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