CA2488704A1 - Titanium and magnesium catalyst component for polymerization of ethylene - Google Patents

Titanium and magnesium catalyst component for polymerization of ethylene Download PDF

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Publication number
CA2488704A1
CA2488704A1 CA002488704A CA2488704A CA2488704A1 CA 2488704 A1 CA2488704 A1 CA 2488704A1 CA 002488704 A CA002488704 A CA 002488704A CA 2488704 A CA2488704 A CA 2488704A CA 2488704 A1 CA2488704 A1 CA 2488704A1
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CA
Canada
Prior art keywords
ethylene
polymerization
homopolymerization
catalyst component
compound
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Granted
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CA002488704A
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French (fr)
Other versions
CA2488704C (en
Inventor
Zhiwu Wang
Zhong Tan
Tianyi Li
Xingbo Li
Kai Zhang
Peng Kou
Haixiang Cui
Zhengyang Guo
Liang Pan
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Individual
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Publication of CA2488704A1 publication Critical patent/CA2488704A1/en
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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
    • 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
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size

Abstract

The present invention provides a catalyst component used for homopolymerization or co-polymerization of ethylene, comprising at least one suitable electron donor compound supported on a composition containing magnesium and titanium, wherein the electron donor compound is selected from the group consisting of aliphatic ethers, alicyclic ethers, aromatic ethers, aliphatic ketones and alicyclic ketones, and wherein the composition containing magnesium and titanium is prepared by dissolving a magnesium compound into a solvent system to form a homogeneous solution and then contacting the solution with a titanium compound in the presence of a precipitation aid to precipitate the composition. The present invention also relates to a method for the preparation of said catalyst component and a catalyst comprising thereof, and to use of the catalyst in homopolymerization of ethylene or co-polymerization of ethylene with at least one C3-C8 .alpha.-olefin.

Claims (25)

What is claimed is:
1. A catalyst component used for homopolymerization or co-polymerization of ethylene, comprising at least one electron donor compound supported on a composition containing magnesium and titanium, wherein the electron donor compound is selected from the group consisting of aliphatic ethers, cyclic ethers, aromatic ethers, aliphatic ketones and alicyclic ketones, and wherein the composition containing magnesium and titanium is prepared by dissolving a magnesium compound into a solvent system to form a homogeneous solution and then contacting the solution with a titanium compound in the presence of a precipitation aid to precipitate the composition.
2. A catalyst component used for homopolymerization or co-polymerization of ethylene, comprising at least one electron donor compound and at least one titanium compound supported on a magnesium compound-containing composition, wherein the electron donor compound is selected from the group consisting of aliphatic ethers, cyclic ethers, aromatic ethers, aliphatic ketones and alicyclic ketones.
3_A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the catalyst component comprises from 5 to 30 percent by weight of magnesium, from 0.1 to 10 percent by weight of titanium, from 15 to 65 percent by weight of halogen, and from 1 to 60 percent by weight of electron donor, based on the total weight of the solid catalyst component;
and the average particle size of the catalyst component, expressed as D50 value, is from 5 to 35 microns.
4. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the titanium compound has a general formula Ti(OR)a X b, in which R is C1_C14 aliphatic hydrocarbyl or aromatic hydrocarbyl, X is halogen, a is 0, 1 or 2, b is an integer of from 1 to 4, and the sum of a + b is 3 or 4.
5. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the magnesium compound is selected from the group consisting of magnesium dihalides, hydrates or alcohol adducts of magnesium dihalide, derivatives formed by replacing one halogen atom of magnesium dihalide with hydrocarbyloxy group or halo-hydrocarbyloxy group, or their mixture.
6. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1, wherein the solvent system comprises an organic epoxy compound and an organophosphorus compound.
7. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 6, wherein the organic epoxy compound comprises at least one selected from the group consisting of oxides of aliphatic olefin, dime or halogenated aliphatic olefin or dime, glycidyl ethers and cyclic ethers having from 2 to 8 carbon atoms.
8. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 6, wherein the organophosphorus compound is at least one selected from the group consisting of hydrocarbyl esters or halohydrocarbyl esters of ortho-phosphoric acid or phosphorous acid.
9. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1, wherein the solvent system comprises a branched aliphatic alcohol compound.
10. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 9, wherein the solvent system comprises 2-ethylhexanol.
11. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1, wherein the precipitation aid is at least one selected from the group consisting of organic carboxylic anhydrides, organic carboxylic acids, ethers and ketones.
12. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1, wherein the precipitation aid is at least one selected from the group consisting of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, 1,2,4,5-benzene tetracarboxylic acid dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether and dipentyl ether.
13_A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the electron donor compound is at least one selected from the group consisting of aliphatic ethers having total from 2 to 12 carbon atoms, cyclic ethers having from 3 to 5 carbon atoms, aromatic ethers having total from 7 to 8 carbon atoms, saturated or unsaturated aliphatic ketones having from 3 to 6 carbon atoms, alicyclic ketones having from 5 to 10 carbon atoms.
14. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the electron donor compound is selected from the group consisting of diethyl ether, di-n-butyl ether, dihexyl ether, ethyl phenyl ether, tetrahydrofuran, acetone, butanone, isobutyl methyl ketone, 4-methyl-3-penten-2-one, hexadione, cyclohexanone and any combinations of any above compounds.
15. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the electron donor compound is a cyclic ether having from 3 to 5 carbon atoms.
16. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein the electron donor compound is tetrahydrofuran.
17. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 1 or claim 2, wherein it further comprises at least one activator having a general formula AlR'c X'd H e, in which R' is saturated hydrocarbyl having 1 to 14 carbon atoms, X' is a halogen, d is 1 or 2, e is 0 or 1, and the sum of c+d+e is 3.
18. A catalyst component used for homopolymerization or co-polymerization of ethylene according to claim 17, wherein the activator is one or more selected from the group consisting of AlEt3, Al(n-Bu)3, Al(n-C6H13)3, Al(i-Bu)3, AlEt2Cl, Al(n-C8H17)3, and AlEt2H.
19. A method for the preparation of a catalyst component used for homopolymerization or co-polymerization of ethylene claimed in claim 1, comprising the steps of:
dissolving a magnesium compound into a solvent system containing an organic epoxy compound and an organophosphorus compound to form a homogeneous solution;
contacting the solution with a titanium compound in the presence of a precipitation aid to precipitate a solid;
treating the obtained solid with an electron donor compound and, optionally, the titanium compound to obtain a product; and optionally, activating the resultant product with an activator.
20. A method according to claim 19, wherein individual raw material can be used in the amount of from 0.2 to 10 mole for the organic epoxy compound, from 0.1 to 3 mole for the organophosphorus compound, from 0.03 to 1.0 mole for the precipitation aid, from 0.5 to 150 mole for the total titanium compound, from 0.01 to mole for the electron donor compound, and from 0.1 to 10 mole for the activator, based on per mole magnesium compound.
21. A catalyst for homopolymerization or co-polymerization of ethylene, comprising the reaction product of the following two components:
(a) catalyst component according to any one of claims 1-18; and (b) organoaluminum as cocatalyst component.
22. A use of the catalyst accoding to claim 21 in homopolymerization of ethylene or co-polymerization of ethylene with at least one C3-C8 .alpha.-olefin.
23. A use of the catalyst according to claim 21 in homopolymerization or co-polymerization of ethylene in gas phase process or slurry process.
24. A method for homopolymerization of ethylene or co-polymerization of ethylene with at least one C3-C8 .alpha.-olefin, comprising contacting ethylene or ethylene and at least one C3-C8 .alpha.-olefin with the catalyst according to claim 21 under polymerization conditions.
25. A method for homopolymerization of ethylene or co-polymerization of ethylene with at least one C3-C8 .alpha.-olefin, comprising contacting ethylene or ethylene and at least one C3-C8 .alpha.-olefin with the catalyst according to claim 21 under polymerization conditions in slurry or gas phase process.
CA2488704A 2002-06-06 2003-06-04 Titanium and magnesium catalyst component for polymerization of ethylene Expired - Lifetime CA2488704C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CNB021208611A CN1194993C (en) 2002-06-06 2002-06-06 Solid catalyst component for ethylene polymerization and catalyst therefor
CN02120861.1 2002-06-06
PCT/CN2003/000436 WO2004033504A1 (en) 2002-06-06 2003-06-04 A solid catalyst component for polymerization of ethylene, preparation thereof and a catalyst containing the same

Publications (2)

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CA2488704A1 true CA2488704A1 (en) 2004-04-22
CA2488704C CA2488704C (en) 2011-10-11

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Country Status (9)

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US (1) US7091289B2 (en)
JP (1) JP2005529230A (en)
KR (1) KR101010668B1 (en)
CN (1) CN1194993C (en)
AU (1) AU2003246109A1 (en)
CA (1) CA2488704C (en)
DE (1) DE10392773B4 (en)
MY (1) MY132100A (en)
WO (1) WO2004033504A1 (en)

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CN102020731B (en) * 2009-09-10 2013-02-27 中国石油化工股份有限公司 Catalyst component for vinyl polymerization and catalyst thereof
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Also Published As

Publication number Publication date
JP2005529230A (en) 2005-09-29
WO2004033504A1 (en) 2004-04-22
MY132100A (en) 2007-09-28
CA2488704C (en) 2011-10-11
US20040030064A1 (en) 2004-02-12
KR20050016498A (en) 2005-02-21
CN1194993C (en) 2005-03-30
US7091289B2 (en) 2006-08-15
KR101010668B1 (en) 2011-01-24
AU2003246109A8 (en) 2004-05-04
DE10392773T5 (en) 2005-08-04
CN1463991A (en) 2003-12-31
DE10392773B4 (en) 2021-07-01
AU2003246109A1 (en) 2004-05-04

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