CA2397401A1 - Polymer control through co-catalyst - Google Patents

Polymer control through co-catalyst Download PDF

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Publication number
CA2397401A1
CA2397401A1 CA002397401A CA2397401A CA2397401A1 CA 2397401 A1 CA2397401 A1 CA 2397401A1 CA 002397401 A CA002397401 A CA 002397401A CA 2397401 A CA2397401 A CA 2397401A CA 2397401 A1 CA2397401 A1 CA 2397401A1
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Canada
Prior art keywords
catalyst
process according
aluminum
group
amount
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Granted
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CA002397401A
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French (fr)
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CA2397401C (en
Inventor
Shivendra Kumar Goyal
Timothy Walter Wiwchar
Victoria Ker
Mark Kelly
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Nova Chemicals Corp
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Nova Chemicals Corp
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Publication of CA2397401C publication Critical patent/CA2397401C/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Some properties such as dart impact strength, hexane extractables and resin stickiness of a polyethylene copolymer produced in a gas phase polymerization using a Ziegler-Natta catalyst are better controlled by regulating the ratio of aluminum from the co-catalyst to the polymer production rate. This enables one to improve properties such as dart impact strength and reduce hexane extractables by changing the amount of co-catalyst fed into the reactor.

Claims (25)

1. In a process for the gas phase polymerization of ethylene and from 0 to 20 weight % of one or more C4-8 copolymerizable alpha olefin monomers in the presence of a supported Zlegler-Natta catalyst co-catalyzed with a co-catalyst selected from the group consisting of tri C2-6 alkyl aluminum, alkyl aluminum halides and mixtures thereof, the improvement of controlling the feed of said co-catalyst to the reactor to provide from 10 to 50 ppm of aluminum from the co-catalyst based on the polymer production rate provided that the molar ratio of total Al from the catalyst and co-catalyst: Ti from the catalyst is not less than 25.1.
2. The process according to claim 1, wherein the co-catalyst is used in an amount to provide from 10 to 40 ppm of aluminum from the co-catalyst based on the polymer production rate.
3. The process according to Claim 2, wherein the Zlegler-Natta catalyst comprises an aluminum compound of the formula Al((O)a R1)b Cl3-b wherein a is either 0 or 1, b is an integer from 1 to 3, R1 is a C1-10 alkyl radical, a titanium compound of the formula Ti(OR2)e X d-c wherein R2 is selected from the group consisting of a C1-4 alkyl radical, a C6-10 aromatic radical, and a radical of the formula -COR3 wherein R3 is selected from the group consisting of a C1-4 alkyl radical and a C6-10 aromatic radical, X
is selected from the group consisting of a chlorine atom and a bromine atom, c is 0 or an integer up to 4 and d is an integer up to 4 and the sum of c+d is the valence of the Ti atom; a magnesium compound of the formula (R5)~ Mg X2-~ wherein each R5 is independently a C1-4 alkyl radical and e is 0, 1 or 2; an alkyl halide selected from the group consisting of CCl4 or a C3-6 secondary or tertiary alkyl halide and optionally an electron donor, said catalyst having a molar ratio of Al to Ti from 1:1 to 15:1; a molar ratio of Mg:Ti from 1:1 to 20:1; a molar ratio of halide from the alkyl halide to Mg from 1:1 to 8:1; a molar ratio of electron donor to Ti from 0:1 to 15:1 and the titanium is present in the catalyst in an amount from 0.25 to 1.25 weight % inclusive of the support.
4. The process according to claim 3, wherein in the catalyst the molar ratio of Al:Ti is from 4:1 to 10:1.
5. The process according to claim 4, wherein in the catalyst the molar ratio of Mg:Ti is from 2:1 to 12:1.
6. The process according to claim 5, wherein in the catalyst the titanium component is selected from the group consisting of TiCl3, TiCl4, Ti(OC4H9)Cl3, Ti(OCOCH3)Cl3 and Ti(OCOC6H5)Cl3.
7. The process according to claim 6, wherein in the catalyst the aluminum compound is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri iso-butyl aluminum, tri-n-hexyl aluminum, tri-octyl aluminum, diethyl aluminum chloride and mixtures thereof.
8. The process according to claim 7, wherein in the catalyst the magnesium compound is selected from the group consisting of magnesium chloride, dibutyl magnesium and butyl ethyl magnesium, provided if the magnesium compound is other than magnesium chloride the alkyl halide is present in an amount to provide a molar ratio of halogen:Mg from 1.5:1 to 6:1.
9. The process according to claim 8, wherein in the catalyst the alkyl halide is a C3-6 secondary or tertiary alkyl chloride.
10. The process according to claim 9, wherein the electron donor is selected from the group consisting of C3-18 linear or cyclic aliphatic or aromatic ethers, ketones, esters, aldehydes, amides, nitriles, amines, phosphines or siloxanes.
11. The process according to claim 10, wherein the support is an inorganic support having an average particle size from about 10 to 150 microns, a surface area greater than 100 m2/g, a pore volume from about 0.3 to 5.0 ml/g, a surface hydroxyl content from about 0.1 to 5 mmol/g of support.
12. The process according to claim 11 ~ wherein the electron donor is present in an amount to provide a molar ratio of electron donor to the titanium from 3:1 to 12:1.
13. The process according to claim 12, wherein the electron donor is selected from the group consisting diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, acetone, ethyl benzoate, and diphenyl ether and mixtures thereof.
14. The process according to claim 13, wherein in the catalyst from 0 to 60 weight % of the aluminum compound of the formula Al((O)a R1)b Cl3-b wherein a is either 0 or 1, b is an integer from 1 to 3, R1 is a C1-8 alkyl radical, is used to treat the support and the aluminum content on the support is included in the ratio of Al:Ti in the catalyst.
15. The process according to claim 14, wherein the remaining aluminum compound in the catalyst is added after the addition of the titanium compound.
16. The process according to claim 15, wherein the titanium compound is selected from the group consisting of TiCl3 and TiCl4.
17. The process according to claim 16, wherein in the catalyst the Ti is present in an amount from 0.25 to 0.70 weight % inclusive of the support.
18. The process according to claim 17, wherein the co-catalyst is triethyl aluminum.
19. The process according to claim 17, wherein the co-catalyst is tri-isobutyl aluminum.
20. The process according to claim 17, wherein the co-catalyst is tri-n-hexyl aluminum.
21. The process according to claim 18, wherein the comonomer is present in an amount from 0.5 to 16 weight % end is selected from the group consisting of butene, 4-methyl pentene, hexene, and a mixture thereof.
22. The process according to claim 21, wherein the comonomer is hexene and is present in an amount from 8 to 13 weight %.
23. The process according to claim 22, wherein the triethyl aluminum is used in an amount to provide from 16 to 31 ppm of aluminum.
24. The process according to claim 19, wherein the comonomer is present in an amount from 0.5 to 16 weight % and is selected from the group consisting of butene, 4-methyl pentene, hexene, and a mixture thereof.
25. The process according to claim 24, wherein the comonomer is hexene and is present in an amount from 8 to 13 weight %.
CA2397401A 2001-08-20 2002-08-19 Polymer control through co-catalyst Expired - Lifetime CA2397401C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/932,883 US6825293B1 (en) 2001-08-20 2001-08-20 Polymer control through co-catalyst
US09/932,883 2001-08-20

Publications (2)

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CA2397401A1 true CA2397401A1 (en) 2003-02-20
CA2397401C CA2397401C (en) 2010-10-12

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CA2397401A Expired - Lifetime CA2397401C (en) 2001-08-20 2002-08-19 Polymer control through co-catalyst

Country Status (8)

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US (1) US6825293B1 (en)
EP (1) EP1285934B1 (en)
KR (1) KR100881268B1 (en)
CN (1) CN1406989B (en)
BR (2) BR0203612B1 (en)
CA (1) CA2397401C (en)
DE (1) DE60215088T2 (en)
ES (1) ES2273973T3 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1652863A1 (en) 2004-10-29 2006-05-03 Nova Chemicals Corporation Enhanced polyolefin catalyst
EP1980506A2 (en) 2007-04-12 2008-10-15 Holtec GmbH & Co.KG Log step feeder
WO2015189725A1 (en) 2014-06-13 2015-12-17 Nova Chemicals (International) S.A. Short chain branching control on ehtylene-butene copolymers
WO2017029579A1 (en) 2015-08-20 2017-02-23 Nova Chemicals (International) S.A. Method for altering melt flow ratio of ethylene polymers

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EP1336625A1 (en) * 2002-02-14 2003-08-20 Novolen Technology Holdings C.V. Solid catalytic component and catalytic system of the Ziegler-Natta type, process for their preparation and their use in the polymerisation of alk-1-enes
CA2524761A1 (en) * 2003-05-12 2005-02-10 Union Carbide Chemicals & Plastics Technology Corporation Process for control of polymer fines in a gas-phase polymerization
KR100771274B1 (en) 2005-12-20 2007-10-29 삼성토탈 주식회사 Catalyst for producing polyolefin having narrow molecular weight distribution and method for producing ethylene c0polymer using the same
EP2003151A1 (en) 2007-06-15 2008-12-17 Nova Chemicals Corporation Improved hydrogen response through catalyst modification
AU2008342371B2 (en) * 2007-12-21 2013-03-07 Basf Se Method for producing a polymer
CA2707171C (en) 2010-06-07 2018-08-14 Nova Chemicals Corporation Increased run length in gas phase reactors
CA2739969C (en) 2011-05-11 2018-08-21 Nova Chemicals Corporation Improving reactor operability in a gas phase polymerization process
US20140178314A1 (en) * 2012-12-19 2014-06-26 The Procter & Gamble Company Compositions and/or articles with improved solubility of a solid active
US10155831B2 (en) * 2013-09-05 2018-12-18 Univation Technologies, Llc Process control for long chain branching control in polyethylene production
JP6853253B2 (en) * 2015-12-09 2021-03-31 ノヴァ ケミカルズ（アンテルナショナル）ソシエテ アノニム Synthesis of Magnesium Dichloride Carrier for AST Offline ZN Catalyst Using Plug Flow Reactor (PFR)
CN106867583B (en) * 2017-04-14 2019-03-05 安徽欧勒奋生物科技有限公司 A kind of efficient method for preparing PAO50 base oil
CA2969627C (en) 2017-05-30 2024-01-16 Nova Chemicals Corporation Ethylene copolymer having enhanced film properties
KR102304973B1 (en) * 2017-11-29 2021-09-24 롯데케미칼 주식회사 Polyethylene, method for preparing the same and separator using the same

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1652863A1 (en) 2004-10-29 2006-05-03 Nova Chemicals Corporation Enhanced polyolefin catalyst
US7211535B2 (en) 2004-10-29 2007-05-01 Nova Chemicals Corporation Enhanced polyolefin catalyst
EP1980506A2 (en) 2007-04-12 2008-10-15 Holtec GmbH & Co.KG Log step feeder
WO2015189725A1 (en) 2014-06-13 2015-12-17 Nova Chemicals (International) S.A. Short chain branching control on ehtylene-butene copolymers
WO2017029579A1 (en) 2015-08-20 2017-02-23 Nova Chemicals (International) S.A. Method for altering melt flow ratio of ethylene polymers
US10087267B2 (en) 2015-08-20 2018-10-02 Nova Chemicals (International) S.A. Method for altering melt flow ratio of ethylene polymers
US10836851B2 (en) 2015-08-20 2020-11-17 Nova Chemicals (International) S.A. Method for altering melt flow ratio of ethylene polymers

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Publication number Publication date
CN1406989B (en) 2010-05-26
BR0203850A (en) 2003-05-20
KR100881268B1 (en) 2009-02-05
ES2273973T3 (en) 2007-05-16
EP1285934A1 (en) 2003-02-26
DE60215088D1 (en) 2006-11-16
CN1406989A (en) 2003-04-02
US6825293B1 (en) 2004-11-30
DE60215088T2 (en) 2007-04-19
EP1285934B1 (en) 2006-10-04
KR20030014657A (en) 2003-02-19
BR0203612B1 (en) 2011-09-20
BR0203612A (en) 2004-08-24
CA2397401C (en) 2010-10-12

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