CZ20012224A3 - Catalyst mixture for polymerization of olefins, polymerization process and polymer produced in such a manner - Google Patents

Catalyst mixture for polymerization of olefins, polymerization process and polymer produced in such a manner Download PDF

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Publication number
CZ20012224A3
CZ20012224A3 CZ20012224A CZ20012224A CZ20012224A3 CZ 20012224 A3 CZ20012224 A3 CZ 20012224A3 CZ 20012224 A CZ20012224 A CZ 20012224A CZ 20012224 A CZ20012224 A CZ 20012224A CZ 20012224 A3 CZ20012224 A3 CZ 20012224A3
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CZ
Czechia
Prior art keywords
group
catalyst
lt
preferably
groups
Prior art date
Application number
CZ20012224A
Other languages
Czech (cs)
Inventor
Rex E. Murray
Simon Mawson
Clark C. Williams
David James Schreck
Original Assignee
Univation Technologies, Llc
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Publication date
Priority to US09/213,627 priority Critical patent/US6320002B1/en
Priority to US09/216,163 priority patent/US6265513B1/en
Priority to US09/216,215 priority patent/US6303719B1/en
Priority to US09/215,706 priority patent/US6268447B1/en
Application filed by Univation Technologies, Llc filed Critical Univation Technologies, Llc
Publication of CZ20012224A3 publication Critical patent/CZ20012224A3/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Abstract

This invention relates to an olefin polymerization catalyst system comprising at least one activator and one of: a) at least two transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, as described below as represented by formula (I), (II), (III) or (IV); b) the product of the combination of an activator and a transition metal catalyst based on bidentate ligands containing pyridine or quinolines moieties, such as those described as represented by formula (III) or (IV), that has been allowed to react prior to the introduction into the reactor, preferably for at least 15 minutes, and/or c) the product of combination of an additive and a transition metal catalyst based on bidentate ligands containing pyridine or quinoline moieties, such as those described below as represented by formula (I) or (II). This invention further relates to a polymer produced therefrom, particularly to unique polyethylene resins, more preferably bimodal high density polyethylene resins produced by this invention.

Description

Technical field

The present invention relates to olefin polymerization catalyst systems comprising activating agents and catalysts based on transition metal compounds including bidentate pyridines containing pyridine or quinoline groups and mixtures thereof, polymerization processes using such catalyst systems and polymers produced by said processes.

BACKGROUND OF THE INVENTION

The intensive commercial use of metallocene catalysts for the production of polyolefins has led to increased interest in the development of non-metallocene catalysts which could be used in homogeneous catalysis. This is more than just an academic interest, since new, non-metallocene catalysts could provide an easier way to products that are already available, as well as the possibility of preparing such products and of manufacturing methods that exceed the capabilities of metallocene of catalysts. In addition, some non-metallocene ligands may be more economically advantageous as it is relatively easy to synthesize various substituted analogs of these ligands.

Therefore, there is a demand in the art for new olefin polymerization catalysts and for unique olefin polymerization catalysts

polymers which could be produced by such catalysts. Further, there is a need for catalyst systems that can be easily modified by adding an additive to a one-component catalyst to form a bimodal product. Further, there is a need for the development of catalysts that can produce both monodal and bimodal polyolefins. The present invention describes a unique group of catalysts, which can be used alone or in a mixture, to prepare unique polyolefins, in particular for the production of bimodal polyethylene.

In published international applications no

WO 96/23101, WO 97/02298, WO 96/33202 and Furhmann et al., Inorg. Chem. 35: 6742-6745 (1996), single nitrogen catalyst systems have been described. US Patent Application Serial No. 09 / 103,620, published as International Application No. WO 99/01460 on January 14, 1999, described the use of transition metal compounds including bidentate ligands containing pyridine or quinoline groups and mixtures thereof with activating agents. in olefin polymerization. In particular, the formation of a gas phase mixture of [[1- (2-pyridyl) N 1 -methylethyl] [1 N-2,6-diisopropylphenylamido]] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzyl with modified methylalumoxane has been described, this mixture allows the preparation of ethylene hexene polymers. In the development of the present invention, it has been found that U.S. Patent Application Serial No. 09 / 103,620 can be modified by directly adding an additive to produce bimodal products from mono-component catalysts.

«• ·

For the purpose of filing a patent application in the United States of America, the following reference materials are incorporated herein: United States Patent Nos. US 4,845,067; US 4,999,327; Japanese Patent No. JP 1126111; U.S. Patent No. 4,508,842 and British Patent Number

UK 1015054.

SUMMARY OF THE INVENTION

The present invention relates to an olefin polymerization catalyst system comprising at least one activating agent and one of the components selected from the group consisting of:

(a) at least two transition metal containing bidentate ligand catalysts containing pyridine or quinoline groups as described below and whose chemical structure may be represented by formulas (I), (II), (III) or (IV) below;

b) mixing the activating agent and a transition metal-containing catalyst based on bidentate pyridines containing pyridine or quinoline groups, such as catalysts of formulas (III) or (IV), the activating agent being reacted with said catalyst before being injected into the reactor, preferably for at least 15 minutes, and / or

(c) the mixing product of the additive and the transition metal containing:

catalysts based on bidentate ligands containing pyridine or quinoline groups, such as catalysts of formulas I or II.

The present invention further relates to a polymer produced by these catalysts, in particular special polyethylene

polymers, preferably bimodal high density polyethylene polymers made according to the present invention.

A. One aspect of the present invention is an olefin polymerization catalyst system comprising at least one activating agent and at least two transition metal containing bidentate ligand catalysts containing pyridine or quinoline groups. The activating agent may be any known catalyst activating agent, and in one embodiment the activating agent is an aluminum alkyl, alumoxane, modified alumoxane, polyalumoxane, non-coordinating anion, Lewis acid, borane, or mixture thereof.

There are many processes for the preparation of alumoxane and modified alumoxanes, and a specific example of such a process is disclosed in U.S. Pat.

US 4,665,208;

US 4,952,540;

US 5,091,352;

US

5,206,199;

US

5,204,419;

US

US

US

4,908,463;

US

4,968,827;

US

US

5,329,032;

US

US

5,235,081;

US

5,157,137;

US

5,103,031;

US

5,391,793;

US

5,391,529;

US

US

5,731,253 a

US

No. 5,731,451, published European patent applications EP-A-0 561 476, EP-A-0 594 218, European patent EP-B1-0 279 586 and published international application WO 94/10180, without limitation the above examples, all of the above-mentioned documents being incorporated herein by reference. Preferably, methylalumoxane, modified methylalumoxane, triisobutylalumoxane and polymethylalumoxane is used as activating agent according to the present invention.

The ionizing compounds (or non-coordinating anions) may contain active hydrogen, or any other cation that is associated but not coordinated or only weakly coordinated with the remaining ion of said ionizing compound. Such compounds and the like have been described in published European patent applications no

EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375

EP-A-0 426 637; EP-A-500 944; EP-A-0 277 003 a

EP-A-0 277 004, in patents

Of United States of America number

US 5,153,157; US 5,198,401;

US 5,066,741; US 5,206,197;

US 5,241,025; US 5,387,568;

US 5,384,299 and US 5,502,124 and in U.S. patent application Ser

No. 08 / 285,380, filed Aug. 3, 1994, the contents of all of the above-cited documents being incorporated herein

A group of other activating agents of the States of America serial number as reference material.

in the published international application, the reagents described in WO 98/07515, the activating agents of which are incorporated herein by reference in their entirety, exemplified by tris (2,2 ', 2' '- nonafluorobiphenyl) fluoroaluminate. The present invention also encompasses the use of mixtures such as mixtures of alumoxanes and reagents as described, for example, in International Applic