CA1312992C - Process for the preparation of a 1-olefin polymer - Google Patents
Process for the preparation of a 1-olefin polymerInfo
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- CA1312992C CA1312992C CA000568466A CA568466A CA1312992C CA 1312992 C CA1312992 C CA 1312992C CA 000568466 A CA000568466 A CA 000568466A CA 568466 A CA568466 A CA 568466A CA 1312992 C CA1312992 C CA 1312992C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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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
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—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
- C08F4/65925—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 two cyclopentadienyl rings being mutually non-bridged
Abstract
ABSTRACT OF THE DISCLOSURE
Process for the preparation of a 1-olefin polymer If the transition metal component used in an olefin poly-merization catalyst is the product of the reaction between a siloxane-substituted metallocene of titanium, zirconium or hafnium and a hydroxyl group-containing support material, for example silicon dioxide, these metallocene catalysts can be employed in existing polymerization plants which are designed for the suspension process.
Process for the preparation of a 1-olefin polymer If the transition metal component used in an olefin poly-merization catalyst is the product of the reaction between a siloxane-substituted metallocene of titanium, zirconium or hafnium and a hydroxyl group-containing support material, for example silicon dioxide, these metallocene catalysts can be employed in existing polymerization plants which are designed for the suspension process.
Description
~ 3 ~
HOECHST AKTIENGESELLSCHAFT HOE 87/F 163 Dr.DA/sch Description Process for the preparation of a 1-olefin polymer The present invention relates to a process for the pre-paration of a 1-olefin polymer using a supported metallo-cene catalyst.
Metallocenes of transition metals are known as catalyst components (cf. US Patent 4,522,982 and US Patent 4,542,199). Together wi~h aluminoxanes, they form homo-geneous transition metal catalysts which are soluble in aromatic hydrocarbons. These catalysts are very active.
~owever, their solubility is a disadvantage if such cata-lysts are to be employed in existing industrial plants since the latter are generally designed for the use of heterogeneous catalyst systems. It was therefore desir-able to find metallocene catalysts ~hich can be used in the form of a suspension.
Metallocene catalysts in which a zirconocene or titanocene component and an aluminoxane are applied together from a solution onto a silicate support are known (cf. European Application Publication 200,794). However, this catalyst system is not very active and has the disadvantage that the ratio between Zr or T; and Al cannot be changed during the polymerization. In addition, the catalyst components are not bound sufficiently strongly to the support and can thus be extracted from the hot suspending agent during 3~ the polymer;zation.
It has no~ been found that these disadvantages can be avoided if only the transition metal compound, in the form of a siloxane-substituted metallocene, is appl;ed to the support.
The invention thus relates to the process described in ~L 3 ~
the claims.
In order to prepare the transition metal component of the catalyst to be used according to the invention, a metal-locene compound is reacted with a hydroxyl group-containing support material.
A metallocene compound of the formula (I) R LCPR5]n Me R5 R7 R7 R9 R2 ~ 16 1 ~ 18 110 ~m (I), in which Me is titanium, zirconium or hafnium, preferably zirconium, and Cp denotes the cyclopent3dienyl ring;
R1 and R2, ;ndependently of one another, are a hydrogen atom, a halogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, preferably an alkyl group or a halogen atom, in particular a chlorine atom;
R3 and R4, independently of one another, denote a hydro-gen atom, a halogen atom, a C1-C4-alkyl group, a C1-C4-alkoxy group, a C6-C1û-aryl group or a C2-C6-alkenoxy group, preferably a hydrogen atom or methyl, ;n particular a hydrogen atom;
R5 and R6, independently of one another~ are a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, preferably an alkyl group, in particular ~ethyl;
R7 and R8, independently of one another, are a hydrogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, pre-ferably an alkyl group or a hydrogen atom, in part;cular a hydrogen atom;
~ . ~
~ 3 ~ C~
R9 and R10, independently of one another, denote a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, preferably an alkyl group, in particular methyl;
S R11 is a C1-C4-alkyl group, preferably ethyl;
m denotes 1 or 2, preferably 1, n ;s 2 - m, o is zero or 1, preferably 1, p is a number from zero to 6, preferably 1, q is zero or 1, preferably zero, and r is a number from zero to 6, preferably 1, ;s used.
Examples of suitabLe metallocene compounds of the formula t1) are 1 ~ C12Z r [~ Si ( CH3 )2-C2H5~
HOECHST AKTIENGESELLSCHAFT HOE 87/F 163 Dr.DA/sch Description Process for the preparation of a 1-olefin polymer The present invention relates to a process for the pre-paration of a 1-olefin polymer using a supported metallo-cene catalyst.
Metallocenes of transition metals are known as catalyst components (cf. US Patent 4,522,982 and US Patent 4,542,199). Together wi~h aluminoxanes, they form homo-geneous transition metal catalysts which are soluble in aromatic hydrocarbons. These catalysts are very active.
~owever, their solubility is a disadvantage if such cata-lysts are to be employed in existing industrial plants since the latter are generally designed for the use of heterogeneous catalyst systems. It was therefore desir-able to find metallocene catalysts ~hich can be used in the form of a suspension.
Metallocene catalysts in which a zirconocene or titanocene component and an aluminoxane are applied together from a solution onto a silicate support are known (cf. European Application Publication 200,794). However, this catalyst system is not very active and has the disadvantage that the ratio between Zr or T; and Al cannot be changed during the polymerization. In addition, the catalyst components are not bound sufficiently strongly to the support and can thus be extracted from the hot suspending agent during 3~ the polymer;zation.
It has no~ been found that these disadvantages can be avoided if only the transition metal compound, in the form of a siloxane-substituted metallocene, is appl;ed to the support.
The invention thus relates to the process described in ~L 3 ~
the claims.
In order to prepare the transition metal component of the catalyst to be used according to the invention, a metal-locene compound is reacted with a hydroxyl group-containing support material.
A metallocene compound of the formula (I) R LCPR5]n Me R5 R7 R7 R9 R2 ~ 16 1 ~ 18 110 ~m (I), in which Me is titanium, zirconium or hafnium, preferably zirconium, and Cp denotes the cyclopent3dienyl ring;
R1 and R2, ;ndependently of one another, are a hydrogen atom, a halogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, preferably an alkyl group or a halogen atom, in particular a chlorine atom;
R3 and R4, independently of one another, denote a hydro-gen atom, a halogen atom, a C1-C4-alkyl group, a C1-C4-alkoxy group, a C6-C1û-aryl group or a C2-C6-alkenoxy group, preferably a hydrogen atom or methyl, ;n particular a hydrogen atom;
R5 and R6, independently of one another~ are a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, preferably an alkyl group, in particular ~ethyl;
R7 and R8, independently of one another, are a hydrogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, pre-ferably an alkyl group or a hydrogen atom, in part;cular a hydrogen atom;
~ . ~
~ 3 ~ C~
R9 and R10, independently of one another, denote a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, preferably an alkyl group, in particular methyl;
S R11 is a C1-C4-alkyl group, preferably ethyl;
m denotes 1 or 2, preferably 1, n ;s 2 - m, o is zero or 1, preferably 1, p is a number from zero to 6, preferably 1, q is zero or 1, preferably zero, and r is a number from zero to 6, preferably 1, ;s used.
Examples of suitabLe metallocene compounds of the formula t1) are 1 ~ C12Z r [~ Si ( CH3 )2-C2H5~
2 . C12Zr [~ ¦~Si ( CH3 )2-OC2~5 ¦
3~ C12Zr [~Cli2Sl(OC2H5)3~
4 C12Z r [~CH2S l ( C1~3 ) ( 0-1-C3~7 ) 2 ~ 2 5 C12Zr [~cl~2-al(C~3)2-()-1-C3~7:
6- C12Zr [~ (t C4Hg)2 OC2Hs¦
_ 4 _ L3~ 2 7 ' C12Z r [~ Si ( C6H5 )2 C2ll5]
_ 4 _ L3~ 2 7 ' C12Z r [~ Si ( C6H5 )2 C2ll5]
8- C12Zr [~si(C2H5)2-c2H5 9. C12Zr [~si(cs3)2-(cs2)6-si(cll3)2-oc2 10~ C12Zr [~CS2Bi(CH3)2-0c2H5]
2 0 1 1 ' C12Z S [g~ C~2-C S2~C52-C112-Si ( CH3 ) 2- 0C 2115 12. C12Ti [~si(ci3)2-C255 13. C12,ri~[~si(CS3)2-OC2H5 14. C12Si`[~Si(cs3)2-oc2li5~
Of these compounds, preferred compounds are Nos. 1, 2~ 3 and 4, inparticular No. 2.
Compounds of this type are described in I.B.L. Booth, G.C. Ofume, C. Stacey and P.J.T. Tait in J. Organomet.
Chem. 315 (1~86), pp. 143-156, and R. Jackson, _ 5 ~3~2~
J. Ruddlesden, D.J. Thomson and R. Whelan in J. Organomet, Chem. 125 (1977), pp. 57-~2~
Suitable support materials are inorganic oxides, carbo-nates such as chalk, silicates such as ta~c, and polymers having hydroxyl groups at the surface. Particularly su;table supports are porous oxides or mixed oxides of silicon and/or aluminum which have a specific surface area of 50 to 1,000 m2/g, preferably 100 to 800, in particular 150 to 650, and whose pore volume is in the range 0.2 to 3, preferably 0.4 to 3, in particular 0.6 to 2~7, cm3/g. The particle si~e is 1 to 500 ~m, prefer-ably 10 to 200 ~m, in part;cular 20 to 100 pm. Depending on the specific surface area and the temperature pre-treatment, the hydroxyl group number is in the range 0.5 to 50 mmol, preferably 1 to Z0, in particular 1.5 to 10, hydroxyl groups per gram of support. Some such oxides are prepared specifically for use as supports for support-;ng catalysts and are commercially available.
Before reacting the support with the metallocene compound, ;t ;s necessary to remove adsorptively bound water by drying at a temperature from 120 to 800C, preferably 200 to 500C, which may take 1 to 10 hours. The drying is monitored analytically by titrating the OH content of the suppûrt material against n-butylmagnesium chloride. After dry;ng, the support is stored under an inert gas, for example nitrogen or argon, with exclusion of air and water.
The support is reacted with the metallocene compound by suspending the support in the inert solvent and heating the dissol~ed metallocene compound at a temperature of 0 to 40Cr preferably 15 to 25C, for 1 to 1,260 minutes, preferably 20 to 180 minutes. The ratio between the metallocene compound and the support is chosen as- a func-tion of the hydroxyl group content so that 10 to 400, preferably 200 to 250, mmol of metallocene compound are employed per 100 grams of support.
- 6 _ ~ ~12~
Suitable solvents are a~l solvents which can be used for olefin polymerization, thus, for example, aliphatic or cycloaliphatic hydrocarbons, for example pentane, hexane, heptane, cyclohe~ane and methylcyclohexane, aromatic hy-drocarbons, such as benzene, toluene, xylene and/or petro-leum or hydrogenated dieseL oil fractions which have been carefully freed from oxygen, sulfur compounds and moisture.
Aliphatic and cycloaliphatic hydrocarbons are preferably used.
The second component of the catalyst according to the in-vention is an aluminoxane of the formula (II) R12 rR12 1 R12 R12~ tA - ~ Al~ (II) for the linear type and/or of the formula (III) rR12 l (III) _ -Al - O- _ ~+2 for the cyclic type. In these formulae, R12 denotes a C1-C6-alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and s denotes an integer from 2 to 40~ preferably 10 to 20~
The aluminoxane can be prepared in various ways.
In one of the processes, finely powdered copper sulfate pentahydrate is slurried in toluene, and sufficient alumi-num trialkyl so that about 1 mole of CuS04.5HzO is available far each 4 Al atoms is added at about -20C in a glass flask under an inert gasO After slow hydrolysis w;th el;m;nation of alkane, the reaction mixture is left at room temperature for 24 to 48 hours, cooling possibly being necessary so that the temperature does not exceed 30C. The copper sulfate ;s subsequently filtered off ~ 2~
from the aluminoxane dissolved in the toluene, and the toluene is removed by vacuum distillation. It is assumed that, in th;s preparation process, the low-molecular-weight a~uminoxanes condense to form higher oligomers with S elimination of aluminum trialkyL.
Furthermore~ aluminoxanes are obtained when aluminum tri-alkyl, preferably aluminum alkyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted wi~h aluminum salts, preferably aluminum sulfate, containing water of crystallization, at a temperature of -20 to 100C. The ratio by volume between the solvent and the aluminum alkyl used ;s 1:1 to 50:1, preferably 5:1, and the reaction time, which can be monitored by the elimination of alkane, can be 1 to Z00 hours, preferabLy 10 to 40 hours.
Of the aluminum salts containing water of crystallization, those are used in particular which have a high content of water of crystallization. Aluminum sulfate hydrate is particularly preferred, above all the compounds Al2(S04)3.18H20 and Al2(S04)3.16HzO having the particularly high content of water of crystallization of 18 or 16 moles of H20 per mole of Al2(S04)3.
The catalyst to be used according to the invention is em-ployed for polymerization of 1-olefins of the formula R-CH=CH2 in which R is hydrogen or a straight-chain or branched alkyl radical having 1 to 12 carbon atoms, pre-ferably 1 to 6 carbon atoms, for example ethylene, propy-lene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.
Ethylene and propylene are particularly preferred.
The polymerization is carr;ed out in a known manner in suspens;on or ;n the gas phase, cont;nuously or batch~ise, in one step or in a number of steps, at a temperature of 0 to 100C, preferably 70 to 90C. The pressure ;s 0.5 to 64 bar. The polymeri~ation is preferred in the indus-tr;alLy particularly important pressure range 5 to 64 bar.
- 8 - ~ 3 ~
In the polymerization, the transition metal component is used in a concentration~ relative to the transition metal, of 10 3 to 10 6, preferably 10 4 to 10 6, moles of Ti, Zr or Hf per liter of solvent or per liter of reactor volume. The aluminoxane is used in a concentration of 10 4 to 10 1, preferably 10 3 to 2 x 10 2, moles per liter of solvent or per liter of reactor volume, relative to the content of aluminum. In principle, however, higher con-centrations are also possible.
The polymerizat;on is carried out in an inert solvent which is customary for the ~iegler low-pressure process, for example in an aliphatic or cycloaliphatic hydrocarbon;
butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane may be mentioned as examples of such solvents. It is also possible to use a petroleum or hydrogenated diesel oil fraction which has been carefully freed from oxygen, sulfur compounds and moisture. Toluene can also be used. Finally, it is also possible to employ ~0 the monomers to be polymerizaed as solvents or suspending agents. The molecular weight of the polymer can be regu-lated in a known fashion; hydrogen is preferably used for this purpose.
The catalyst to be used according to the invention is distingu;shed by the fact that the transition metal com-pound is strongly bound to the support material. It has been possible to show that alcohol is formed during the reaction of the metallocene compound with the support material, for example in accordance with the following equation:
~3~2~
~OH + H5C20-Si (GH3)2 S ~ ~ Zr~1 support surface 1 n ~o - S~ ( CH3 ) 2 ~1~
ZrC12 ~ C2H5 Extremely high yields are achieved with the aid of the catalyst to be used according to the ;nvent;on.
The follow;ng Examples are intended to illustrate the invention.
Example 1 (Preparation of a preferred metallocene~
Cyclopentadienyl[(d;methylethoxys;lyl)cyclopentadienyl]-zirconium dichloride 9.36 9 (43.35 mmol) of potassium dimethylethoxysilylcyclo-pentadienide in 30 cm3 of tetrahydrofuran were added dropwise at -50C to a suspension of 11.3 9 (43.0~ mmol) of cyclopentadienylzirconium trichloride in 100 cm3 of tetrahydrofuran within 1 hour. After stirr;ng at -20C
for 2 hoùrs, the batch was warmed to room temperature and stirring was continued overnight. The batch was filtered, the f;ltrate was evaporated, and the residue was extracted with pentane. ~hite needles crystallized from the fil-tered and concen~rated pentane extract on cooling and were separated off, washed with cold pentane and dried in YaCuo .
~- . ,.
' ~
:
~ 3 ~ 3 s~
Yield 3.75 9 (7.55 mmol = 34% of theory) Elemental analysis and H NMR spectrum were consistent with the structure given above.
Example 2 5.47 9 of silicon dioxide (0.88 mmol of OH groups/g) were suspended in 30 cm3 of toluene. 0.9 9 (2.28 mmol) of C~2Zr(C5H5)(CsH4-Si(CH3)2-OC2Hs)~ dissolved in 20 ml of toluene, was added at 0C over 15 minutes.
When the batch had warmed to room temperature, ;t was stirred for a further 14 hours. The solid was separated off, washed three times with 20 cm3 of diethyl ether in each case and dried in vacuo. In order to remove metal-locene which was not chemically bound, the solid was extracted for 24 hours in a Soxhlet apparatus using ben-zene and subsequently dried in a high vacuum. Zr content 2.7~ by weight.
Example 3 750 cm3 of a diesel oil fraction (b.p. 100 to 120C) were introduced into a 1 dm3 polymerization reactor and heated to 70C. The reactor was charged with 6.4 cm3 of a methyl aluminoxane solut;on containing 0.22 mmol of alumi-num, and with 67 mg (0.02 mmol of Zr) of the transition metal component from Example 2 in 10 cm3 of solvent.
Ethylene was then passed in to a final pressure of 7 bar and polymerized for 1 hour. 60.6 9 of polyethylene cor-kg responding to 3.05 mmol of Zr x h, were obtained. The product obtained had ~he following data:
MFI 19ût21.6 0.09 9/10 min Viscosity No. 600 cm3/g Density 0~946 g/cm3.
Example 4 The procedure carried out was as in Example 3, but the amount of transition metal component used was now 0.01 mmol, relative to zirconium.
~ 3 ~
Yield 42 9; MFI 190/21.6 0.09 9/10 min Viscosity No. 600 cm3/g Density 0.946 g/cm3 Catalyst yield 4.2 kg/mmol Example 5 The procedure carried out was as in Example 3, but 9.8 cm3 of 1-butene (106 mmol) were introduced into the reactor after addition of the catalyst components and the ethylene pressure was subsequently restored to 7 bar.
Yield 36 9; MFI 190/21.6 0.15 9/10 min Viscosity No. 400 cm3/g Dens;ty 0.942 g/cm3 Catalyst yield 1.8 kg/mmol Comparative EXample A
The yield ~as calculated from the data in EP 206,794 (Example 1); it is considerably below the level of the examples according to the invention.
Zirconium concentration (mmol) 0.034 Aluminum concentration (mmol of Al) 0.83 Aluminum:~irconium (mol:mol) 24.4 Ethylene pressure (bar) 13.8 Temperature (C) 85 Yield (kg) 0.0123 Catalyst yield (kg/mmol of Zr) 0.36 E~ample 6 The procedure carried out was as in Example 3, but the Zr transition metal component was replaced by the analagous T; component in an amount of 40 mg (0.02 mmol of Ti). The T; content of the component was 2.4% by weight.
Yield 28 9 of PE, corresponding to a calculated yield of 1.4 kg of PE/mmol of Ti.
MFI 190C~21.6 0.07 9/10 min V;scos;ty number 720 cm3/g Density 0.948 g/cm3 . ' ' - 12 - 1312~
Example 7 The procedure carried out was as in Example 3, but the Zr transition metal component was replaced by the analagous Hf component in an amount of 137 mg (0.02 mmol of Hf).
The Hf content of the component was 2.6% by weight.
Y;eld 12 g of PE, correspond;ng to a catalyst y;eld of 0.6 kg of PE/mmol of Hf.
MFI 190C/Z1.6 0.06 9/10 m;n Viscosity number 810 cm3/g 10 Density 0.947 g/cm3 .
2 0 1 1 ' C12Z S [g~ C~2-C S2~C52-C112-Si ( CH3 ) 2- 0C 2115 12. C12Ti [~si(ci3)2-C255 13. C12,ri~[~si(CS3)2-OC2H5 14. C12Si`[~Si(cs3)2-oc2li5~
Of these compounds, preferred compounds are Nos. 1, 2~ 3 and 4, inparticular No. 2.
Compounds of this type are described in I.B.L. Booth, G.C. Ofume, C. Stacey and P.J.T. Tait in J. Organomet.
Chem. 315 (1~86), pp. 143-156, and R. Jackson, _ 5 ~3~2~
J. Ruddlesden, D.J. Thomson and R. Whelan in J. Organomet, Chem. 125 (1977), pp. 57-~2~
Suitable support materials are inorganic oxides, carbo-nates such as chalk, silicates such as ta~c, and polymers having hydroxyl groups at the surface. Particularly su;table supports are porous oxides or mixed oxides of silicon and/or aluminum which have a specific surface area of 50 to 1,000 m2/g, preferably 100 to 800, in particular 150 to 650, and whose pore volume is in the range 0.2 to 3, preferably 0.4 to 3, in particular 0.6 to 2~7, cm3/g. The particle si~e is 1 to 500 ~m, prefer-ably 10 to 200 ~m, in part;cular 20 to 100 pm. Depending on the specific surface area and the temperature pre-treatment, the hydroxyl group number is in the range 0.5 to 50 mmol, preferably 1 to Z0, in particular 1.5 to 10, hydroxyl groups per gram of support. Some such oxides are prepared specifically for use as supports for support-;ng catalysts and are commercially available.
Before reacting the support with the metallocene compound, ;t ;s necessary to remove adsorptively bound water by drying at a temperature from 120 to 800C, preferably 200 to 500C, which may take 1 to 10 hours. The drying is monitored analytically by titrating the OH content of the suppûrt material against n-butylmagnesium chloride. After dry;ng, the support is stored under an inert gas, for example nitrogen or argon, with exclusion of air and water.
The support is reacted with the metallocene compound by suspending the support in the inert solvent and heating the dissol~ed metallocene compound at a temperature of 0 to 40Cr preferably 15 to 25C, for 1 to 1,260 minutes, preferably 20 to 180 minutes. The ratio between the metallocene compound and the support is chosen as- a func-tion of the hydroxyl group content so that 10 to 400, preferably 200 to 250, mmol of metallocene compound are employed per 100 grams of support.
- 6 _ ~ ~12~
Suitable solvents are a~l solvents which can be used for olefin polymerization, thus, for example, aliphatic or cycloaliphatic hydrocarbons, for example pentane, hexane, heptane, cyclohe~ane and methylcyclohexane, aromatic hy-drocarbons, such as benzene, toluene, xylene and/or petro-leum or hydrogenated dieseL oil fractions which have been carefully freed from oxygen, sulfur compounds and moisture.
Aliphatic and cycloaliphatic hydrocarbons are preferably used.
The second component of the catalyst according to the in-vention is an aluminoxane of the formula (II) R12 rR12 1 R12 R12~ tA - ~ Al~ (II) for the linear type and/or of the formula (III) rR12 l (III) _ -Al - O- _ ~+2 for the cyclic type. In these formulae, R12 denotes a C1-C6-alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and s denotes an integer from 2 to 40~ preferably 10 to 20~
The aluminoxane can be prepared in various ways.
In one of the processes, finely powdered copper sulfate pentahydrate is slurried in toluene, and sufficient alumi-num trialkyl so that about 1 mole of CuS04.5HzO is available far each 4 Al atoms is added at about -20C in a glass flask under an inert gasO After slow hydrolysis w;th el;m;nation of alkane, the reaction mixture is left at room temperature for 24 to 48 hours, cooling possibly being necessary so that the temperature does not exceed 30C. The copper sulfate ;s subsequently filtered off ~ 2~
from the aluminoxane dissolved in the toluene, and the toluene is removed by vacuum distillation. It is assumed that, in th;s preparation process, the low-molecular-weight a~uminoxanes condense to form higher oligomers with S elimination of aluminum trialkyL.
Furthermore~ aluminoxanes are obtained when aluminum tri-alkyl, preferably aluminum alkyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted wi~h aluminum salts, preferably aluminum sulfate, containing water of crystallization, at a temperature of -20 to 100C. The ratio by volume between the solvent and the aluminum alkyl used ;s 1:1 to 50:1, preferably 5:1, and the reaction time, which can be monitored by the elimination of alkane, can be 1 to Z00 hours, preferabLy 10 to 40 hours.
Of the aluminum salts containing water of crystallization, those are used in particular which have a high content of water of crystallization. Aluminum sulfate hydrate is particularly preferred, above all the compounds Al2(S04)3.18H20 and Al2(S04)3.16HzO having the particularly high content of water of crystallization of 18 or 16 moles of H20 per mole of Al2(S04)3.
The catalyst to be used according to the invention is em-ployed for polymerization of 1-olefins of the formula R-CH=CH2 in which R is hydrogen or a straight-chain or branched alkyl radical having 1 to 12 carbon atoms, pre-ferably 1 to 6 carbon atoms, for example ethylene, propy-lene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.
Ethylene and propylene are particularly preferred.
The polymerization is carr;ed out in a known manner in suspens;on or ;n the gas phase, cont;nuously or batch~ise, in one step or in a number of steps, at a temperature of 0 to 100C, preferably 70 to 90C. The pressure ;s 0.5 to 64 bar. The polymeri~ation is preferred in the indus-tr;alLy particularly important pressure range 5 to 64 bar.
- 8 - ~ 3 ~
In the polymerization, the transition metal component is used in a concentration~ relative to the transition metal, of 10 3 to 10 6, preferably 10 4 to 10 6, moles of Ti, Zr or Hf per liter of solvent or per liter of reactor volume. The aluminoxane is used in a concentration of 10 4 to 10 1, preferably 10 3 to 2 x 10 2, moles per liter of solvent or per liter of reactor volume, relative to the content of aluminum. In principle, however, higher con-centrations are also possible.
The polymerizat;on is carried out in an inert solvent which is customary for the ~iegler low-pressure process, for example in an aliphatic or cycloaliphatic hydrocarbon;
butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane may be mentioned as examples of such solvents. It is also possible to use a petroleum or hydrogenated diesel oil fraction which has been carefully freed from oxygen, sulfur compounds and moisture. Toluene can also be used. Finally, it is also possible to employ ~0 the monomers to be polymerizaed as solvents or suspending agents. The molecular weight of the polymer can be regu-lated in a known fashion; hydrogen is preferably used for this purpose.
The catalyst to be used according to the invention is distingu;shed by the fact that the transition metal com-pound is strongly bound to the support material. It has been possible to show that alcohol is formed during the reaction of the metallocene compound with the support material, for example in accordance with the following equation:
~3~2~
~OH + H5C20-Si (GH3)2 S ~ ~ Zr~1 support surface 1 n ~o - S~ ( CH3 ) 2 ~1~
ZrC12 ~ C2H5 Extremely high yields are achieved with the aid of the catalyst to be used according to the ;nvent;on.
The follow;ng Examples are intended to illustrate the invention.
Example 1 (Preparation of a preferred metallocene~
Cyclopentadienyl[(d;methylethoxys;lyl)cyclopentadienyl]-zirconium dichloride 9.36 9 (43.35 mmol) of potassium dimethylethoxysilylcyclo-pentadienide in 30 cm3 of tetrahydrofuran were added dropwise at -50C to a suspension of 11.3 9 (43.0~ mmol) of cyclopentadienylzirconium trichloride in 100 cm3 of tetrahydrofuran within 1 hour. After stirr;ng at -20C
for 2 hoùrs, the batch was warmed to room temperature and stirring was continued overnight. The batch was filtered, the f;ltrate was evaporated, and the residue was extracted with pentane. ~hite needles crystallized from the fil-tered and concen~rated pentane extract on cooling and were separated off, washed with cold pentane and dried in YaCuo .
~- . ,.
' ~
:
~ 3 ~ 3 s~
Yield 3.75 9 (7.55 mmol = 34% of theory) Elemental analysis and H NMR spectrum were consistent with the structure given above.
Example 2 5.47 9 of silicon dioxide (0.88 mmol of OH groups/g) were suspended in 30 cm3 of toluene. 0.9 9 (2.28 mmol) of C~2Zr(C5H5)(CsH4-Si(CH3)2-OC2Hs)~ dissolved in 20 ml of toluene, was added at 0C over 15 minutes.
When the batch had warmed to room temperature, ;t was stirred for a further 14 hours. The solid was separated off, washed three times with 20 cm3 of diethyl ether in each case and dried in vacuo. In order to remove metal-locene which was not chemically bound, the solid was extracted for 24 hours in a Soxhlet apparatus using ben-zene and subsequently dried in a high vacuum. Zr content 2.7~ by weight.
Example 3 750 cm3 of a diesel oil fraction (b.p. 100 to 120C) were introduced into a 1 dm3 polymerization reactor and heated to 70C. The reactor was charged with 6.4 cm3 of a methyl aluminoxane solut;on containing 0.22 mmol of alumi-num, and with 67 mg (0.02 mmol of Zr) of the transition metal component from Example 2 in 10 cm3 of solvent.
Ethylene was then passed in to a final pressure of 7 bar and polymerized for 1 hour. 60.6 9 of polyethylene cor-kg responding to 3.05 mmol of Zr x h, were obtained. The product obtained had ~he following data:
MFI 19ût21.6 0.09 9/10 min Viscosity No. 600 cm3/g Density 0~946 g/cm3.
Example 4 The procedure carried out was as in Example 3, but the amount of transition metal component used was now 0.01 mmol, relative to zirconium.
~ 3 ~
Yield 42 9; MFI 190/21.6 0.09 9/10 min Viscosity No. 600 cm3/g Density 0.946 g/cm3 Catalyst yield 4.2 kg/mmol Example 5 The procedure carried out was as in Example 3, but 9.8 cm3 of 1-butene (106 mmol) were introduced into the reactor after addition of the catalyst components and the ethylene pressure was subsequently restored to 7 bar.
Yield 36 9; MFI 190/21.6 0.15 9/10 min Viscosity No. 400 cm3/g Dens;ty 0.942 g/cm3 Catalyst yield 1.8 kg/mmol Comparative EXample A
The yield ~as calculated from the data in EP 206,794 (Example 1); it is considerably below the level of the examples according to the invention.
Zirconium concentration (mmol) 0.034 Aluminum concentration (mmol of Al) 0.83 Aluminum:~irconium (mol:mol) 24.4 Ethylene pressure (bar) 13.8 Temperature (C) 85 Yield (kg) 0.0123 Catalyst yield (kg/mmol of Zr) 0.36 E~ample 6 The procedure carried out was as in Example 3, but the Zr transition metal component was replaced by the analagous T; component in an amount of 40 mg (0.02 mmol of Ti). The T; content of the component was 2.4% by weight.
Yield 28 9 of PE, corresponding to a calculated yield of 1.4 kg of PE/mmol of Ti.
MFI 190C~21.6 0.07 9/10 min V;scos;ty number 720 cm3/g Density 0.948 g/cm3 . ' ' - 12 - 1312~
Example 7 The procedure carried out was as in Example 3, but the Zr transition metal component was replaced by the analagous Hf component in an amount of 137 mg (0.02 mmol of Hf).
The Hf content of the component was 2.6% by weight.
Y;eld 12 g of PE, correspond;ng to a catalyst y;eld of 0.6 kg of PE/mmol of Hf.
MFI 190C/Z1.6 0.06 9/10 m;n Viscosity number 810 cm3/g 10 Density 0.947 g/cm3 .
Claims (3)
1. A process for the preparation of a 1-olefin polymer by polymerizing a 1-olefin of the formula R-CH=CH2 in which R is hydrogen or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, at a tempera-ture of -60 to 100°C, at a pressure of 0.5 to 64 bar, in suspension or in the gas phase, in the presence of a catalyst which comprises a transition metal component, which is a transition metal compound located on a sup-port, and an aluminoxane, wherein the polymerization is carried out in the presence of a catalyst whose transition metal component has been prepared by react-ing a metallocene compound of the formula I
(I), in which Me is titanium, zirconium or hafnium, Cp denotes the cyclopentadienyl ring.
R1 and R2, independently of one another, denote a hy-drogen atom, a halogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, R3 and R4, independently of one another, denote a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a C1-C4-alkoxy group, a C6-C10-aryl group or a C2-C6-alkenoxy group, R5 and R6, independently of one another, denote a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, R7 and R8, independently of one another, denote a hydrogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, R9 and R10, independently of one another, denote a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, R11 denotes a C1-C4-alkyl group, m is 1 or 2, n is 2 - m, o is zero or 1, p is a number from zero to o, q is zero or 1, and r is a number from zero to 6, with a hydroxyl group-containing support material, and the aluminoxane is one of the formula II
(II) for the linear type and/or of the formula (III) (III) for the cyclic type, where, in the formulae II and III, R12 denotes a C1-C6-alkyl group and s is an integer from 2 to 40.
(I), in which Me is titanium, zirconium or hafnium, Cp denotes the cyclopentadienyl ring.
R1 and R2, independently of one another, denote a hy-drogen atom, a halogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, R3 and R4, independently of one another, denote a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a C1-C4-alkoxy group, a C6-C10-aryl group or a C2-C6-alkenoxy group, R5 and R6, independently of one another, denote a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, R7 and R8, independently of one another, denote a hydrogen atom, a C1-C4-alkyl group or a C6-C10-aryl group, R9 and R10, independently of one another, denote a C1-C4-alkyl group, a C6-C10-aryl group or a C1-C4-alkoxy group, R11 denotes a C1-C4-alkyl group, m is 1 or 2, n is 2 - m, o is zero or 1, p is a number from zero to o, q is zero or 1, and r is a number from zero to 6, with a hydroxyl group-containing support material, and the aluminoxane is one of the formula II
(II) for the linear type and/or of the formula (III) (III) for the cyclic type, where, in the formulae II and III, R12 denotes a C1-C6-alkyl group and s is an integer from 2 to 40.
2. The process as claimed in claim 1, wherein the tran-sition metal component used is the product of the reaction between a metallocene compound of the formula (I) in which Me is titanium or zirconium, and a metal oxide.
3. The process as claimed in claim 2, wherein the tran-sition metal component is the product of the reaction between a zirconium compound of the formula (I) and silicon dioxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873718888 DE3718888A1 (en) | 1987-06-05 | 1987-06-05 | METHOD FOR PRODUCING A 1-OLEFIN POLYMER |
| DEP3718888.7 | 1987-06-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1312992C true CA1312992C (en) | 1993-01-19 |
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ID=6329146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000568466A Expired - Fee Related CA1312992C (en) | 1987-06-05 | 1988-06-02 | Process for the preparation of a 1-olefin polymer |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0293815B1 (en) |
| JP (1) | JP2609287B2 (en) |
| AU (1) | AU600831B2 (en) |
| CA (1) | CA1312992C (en) |
| DE (2) | DE3718888A1 (en) |
| ES (1) | ES2019123B3 (en) |
| ZA (1) | ZA883948B (en) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3782243T2 (en) * | 1986-08-26 | 1993-03-04 | Mitsui Petrochemical Ind | CATALYST FOR POLYMERIZING ALPHA OLEFIN AND METHOD. |
| DE3640948A1 (en) * | 1986-11-29 | 1988-06-01 | Hoechst Ag | METHOD FOR PRODUCING A 1-OLEFIN STEREOBLOCK POLYMER |
| DE3840772A1 (en) * | 1988-12-03 | 1990-06-07 | Hoechst Ag | METHOD FOR PRODUCING A HETEROGENIC METALLOCENE CATALYST COMPONENT |
| US5262498A (en) * | 1991-01-12 | 1993-11-16 | Hoechst Aktiengesellschaft | Metallocene (co)polymers, process for their preparation and their use as catalysts |
| US5169818A (en) * | 1991-01-12 | 1992-12-08 | Hoechst Aktiengesellschaft | Metallocene (co)polymers, process for their preparation and their use as catalysts |
| TW218884B (en) * | 1991-05-01 | 1994-01-11 | Mitsubishi Kakoki Kk | |
| US5466766A (en) * | 1991-05-09 | 1995-11-14 | Phillips Petroleum Company | Metallocenes and processes therefor and therewith |
| US5399636A (en) * | 1993-06-11 | 1995-03-21 | Phillips Petroleum Company | Metallocenes and processes therefor and therewith |
| WO1993011172A1 (en) * | 1991-11-25 | 1993-06-10 | Exxon Chemical Patents Inc. | Polyonic transition metal catalyst composition |
| FR2725993B1 (en) * | 1994-10-21 | 1996-11-29 | Atochem Elf Sa | SOLID CATALYTIC COMPONENT CONTAINING ZIRCONIUM AND CYCLOALCADIENYL GROUPS, PROCESS FOR OBTAINING SAME AND PROCESS FOR POLYMERIZATION OF OLEFINS IN ITS PRESENCE |
| CN1047388C (en) * | 1995-07-14 | 1999-12-15 | 中国石油化工总公司 | Prepn of carried type metallocene compound/aluminoxyane catalyst |
| DE19527652A1 (en) * | 1995-07-28 | 1997-01-30 | Hoechst Ag | Metallocene compound |
| ES2120868B1 (en) * | 1995-08-03 | 2000-09-16 | Repsol Quimica Sa | METALOGEN TYPE HETEREOGENEOUS CATALYST SYSTEM, FOR PROCESSES OF OBTAINING POLYOLEFINS. |
| AU2328497A (en) * | 1996-03-05 | 1997-09-22 | Massachusetts Institute Of Technology | Group 4 metal-containing organosilicon dendrimers |
| US6313239B1 (en) * | 1996-03-05 | 2001-11-06 | Bayer Corporation | Olefin polymerization with group 4 metal-containing organosilicon dendrimers |
| FI961511A (en) * | 1996-04-03 | 1997-10-04 | Mikrokemia Oy | Process for the preparation of olefin polymerization catalysts |
| ES2129323B1 (en) * | 1996-04-18 | 2000-09-16 | Repsol Quimica Sa | PROCEDURE FOR OBTAINING A CATALYTIC SYSTEM FOR THE POLYMERIZATION OF ALPHA-OLEFINS IN SUSPENSION IN GAS PHASE AT LOW AND HIGH TEMPERATURES OR IN MASS AT HIGH PRESSURES AND HIGH OR LOW TEMPERATURES |
| IT1283010B1 (en) * | 1996-05-15 | 1998-04-03 | Enichem Spa | SUPPORTED METALLOCENE COMPLEX AND PROCEDURE FOR ITS PREPARATION |
| KR100205738B1 (en) * | 1996-07-26 | 1999-07-01 | 이정국 | Supported catalyst and process for preparing the same |
| PT839834E (en) * | 1996-10-30 | 2001-11-30 | Repsol Quimica Sa | ORGANOMETHALIC CATALYSTS AND THEIR USE FOR POLYMERIZATION AND COPOLYMERIZATION OF ALPHA-OLEFINS |
| ES2158474T3 (en) | 1996-10-30 | 2001-09-01 | Repsol Quimica Sa | CATALYZER SYSTEMS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ALFA-OLEFINS. |
| US20030195109A1 (en) | 1996-10-31 | 2003-10-16 | Jose Sancho Royo | Catalytic systems for the polimerisation and copolimerisation of alpha-olefins |
| EP0856524A1 (en) | 1997-02-01 | 1998-08-05 | Repsol Quimica S.A. | Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof |
| US6177375B1 (en) * | 1998-03-09 | 2001-01-23 | Pq Corporation | High activity olefin polymerization catalysts |
| KR100358225B1 (en) | 1998-04-09 | 2003-01-24 | 주식회사 엘지화학 | Polymerization method using metallocene enabling cocatalyst to be recirculated |
| KR100380018B1 (en) * | 1998-04-09 | 2003-10-04 | 주식회사 엘지화학 | Supported metallocene catalyst and olefin polymerization method using the catalyst |
| ES2211013T3 (en) * | 1998-04-27 | 2004-07-01 | Repsol Quimica S.A. | CATALYTIC SYSTEMS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ALFA-OLEFINS. |
| ATE231515T1 (en) * | 1998-04-29 | 2003-02-15 | Repsol Quimica Sa | FUNCTIONALIZED METALLOCENES, THEIR PRODUCTION AND THEIR USE |
| KR100367463B1 (en) * | 1999-03-03 | 2003-01-14 | 주식회사 엘지화학 | Metallocene compounds and their use for olefin polymerization |
| US6194343B1 (en) * | 1999-03-11 | 2001-02-27 | University Of Waterloo | Bridged “tethered” metallocenes |
| JP4622045B2 (en) * | 1999-06-03 | 2011-02-02 | 株式会社豊田中央研究所 | Polymerization catalyst and resin composite synthesis method |
| KR100354290B1 (en) * | 1999-06-22 | 2002-09-28 | 주식회사 엘지화학 | Supported metallocene catalysts and their use for olefin polymerization |
| US7247595B2 (en) | 1999-06-22 | 2007-07-24 | Lg Chem, Ltd. | Supported metallocene catalyst and olefin polymerization using the same |
| US7041618B2 (en) * | 1999-06-22 | 2006-05-09 | Lg Chemical Ltd. | Supported metallocene catalyst and olefin polymerization using the same |
| TW548283B (en) * | 2000-01-11 | 2003-08-21 | Dow Chemical Co | Chemically-modified supports and supported catalyst systems prepared therefrom |
| ES2217104T3 (en) | 2001-01-18 | 2004-11-01 | Repsol Quimica S.A. | OLEFIN POLYMERIZATION CATALYSTS. |
| KR100690345B1 (en) * | 2004-09-03 | 2007-03-09 | 주식회사 엘지화학 | Supported metallocene catalyst using the metallocene compound, method for preparing the same and method for manufacturing polyolefins using the same |
| EP2070953A1 (en) | 2007-12-11 | 2009-06-17 | Total Petrochemicals Research Feluy | Activating supports based on phosphonium complexes |
| WO2009151507A2 (en) * | 2008-04-28 | 2009-12-17 | Univation Technologies, Llc | Methods for preparing catalyst systems |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1268754A (en) * | 1985-06-21 | 1990-05-08 | Howard Curtis Welborn, Jr. | Supported polymerization catalyst |
-
1987
- 1987-06-05 DE DE19873718888 patent/DE3718888A1/en not_active Withdrawn
-
1988
- 1988-05-31 EP EP88108658A patent/EP0293815B1/en not_active Expired - Lifetime
- 1988-05-31 ES ES88108658T patent/ES2019123B3/en not_active Expired - Lifetime
- 1988-05-31 DE DE8888108658T patent/DE3860988D1/en not_active Expired - Fee Related
- 1988-06-02 CA CA000568466A patent/CA1312992C/en not_active Expired - Fee Related
- 1988-06-03 ZA ZA883948A patent/ZA883948B/en unknown
- 1988-06-03 AU AU17320/88A patent/AU600831B2/en not_active Ceased
- 1988-06-03 JP JP63135729A patent/JP2609287B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3860988D1 (en) | 1990-12-13 |
| ES2019123B3 (en) | 1991-06-01 |
| EP0293815B1 (en) | 1990-11-07 |
| EP0293815A1 (en) | 1988-12-07 |
| ZA883948B (en) | 1989-02-22 |
| AU1732088A (en) | 1988-12-08 |
| DE3718888A1 (en) | 1988-12-22 |
| AU600831B2 (en) | 1990-08-23 |
| JP2609287B2 (en) | 1997-05-14 |
| JPS63312303A (en) | 1988-12-20 |
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