WO2001044313A1 - Procede d'elaboration de catalyseur supporte pour la polymerisation d'ethylene et la copolymerisation d'ethylene/alpha-olefine - Google Patents

Procede d'elaboration de catalyseur supporte pour la polymerisation d'ethylene et la copolymerisation d'ethylene/alpha-olefine Download PDF

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Publication number
WO2001044313A1
WO2001044313A1 PCT/KR2000/001456 KR0001456W WO0144313A1 WO 2001044313 A1 WO2001044313 A1 WO 2001044313A1 KR 0001456 W KR0001456 W KR 0001456W WO 0144313 A1 WO0144313 A1 WO 0144313A1
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WO
WIPO (PCT)
Prior art keywords
compound
organic
polymerization
ethylene
silicon
Prior art date
Application number
PCT/KR2000/001456
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English (en)
Inventor
Ho-Sik Chang
Sung-Gun Roh
Gyo-Hyun Hwang
Original Assignee
Samsung General Chemicals, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Samsung General Chemicals, Ltd. filed Critical Samsung General Chemicals, Ltd.
Priority to AU20293/01A priority Critical patent/AU2029301A/en
Publication of WO2001044313A1 publication Critical patent/WO2001044313A1/fr

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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
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof

Definitions

  • the present invention relates to a preparation method of catalyst for polymerization of ethylene and co-polymerization of ethylene and alpha-olefin, and in particular, to a preparation method of supported catalyst containing titanium compound on the carrier, which contains magnesium and has narrow particle size distribution.
  • the catalyst produced by the above method especially the catalyst obtained by the method of covering TiCl 4 on the carrier, has narrow particle size distribution and high bulk density and achieved partial improvement in polymerization process, it still has the disadvantage that the distribution of the molecular weights is not still sufficiently narrow, and high initial catalytic activity and particle size control is still difficult to achieve.
  • the method of preparing catalyst with uniform active site that can get narrow molecular weight distribution, and the method of controlling polymer particle size as needed in the application of the product or in the polymerization process is demanded.
  • the object of the present invention is to provide a method of manufacturing polymers with narrow molecular weight distribution and higher bulk density, and to provide the preparation method of catalyst for polymerization of ethylene, and co-polymerization of ethylene and alpha-olefin in slurry and gas phase polymerization in which polymer particle size is easily controlled for the productivity of polymerization process and for various application.
  • organic magnesium complex agent [MgPh9.nMgCl 2 .mR 2 O] which forms a solution dissolved in solvent chlorobenzene, ether(R 2 ⁇ ), or the mixture of chlorobenzene and ether, or the mixture of chlorobenzene and aliphatic or aromatic compound is used in the step of producing magnesium containing carrier.
  • carrier containing powder organic magnesium suspended in the hydrocarbon solution is produced by reacting said solution of organic magnesium compound with organic chlorine compound and silicon compound with a molar ratio of (organic chlorine compoundVMg ⁇ 0.5 and (silicon compoundVMg ⁇ 0.001 at the temperature of - 20-80 ° C .
  • Carrier obtained by said method has narrow distribution of particle size.
  • the size of carrier and catalyst particles can be controlled within 5- 150 m by the molar ratio of silicon compound to magnesium, and the reaction condition of organic magnesium compound and organic chlorine compound.
  • the magnesium containing carrier obtained by the said method includes mainly magnesium dichloride(80 ⁇ 90 weight%), ether(7 ⁇ 15 weight%), siliconOess than 1 weight%) and hydrocarbon complex compoundd — 5 weight%).
  • organic magnesium compound used in the production of magnesium containing carrier is produced by reacting powder magnesium with chlorobenzene in the presence of one or more of electron donor, wherein the electron donor can include aliphatic or cyclic ether.
  • Aliphatic ether which has chemical formula of R2OR3, wherein R2 and R3 can be the same or different alkyl radical having 2-8 of carbons, preferably having 4-5 carbon atoms.
  • Cyclic ether has the carbon numbers of 3-5.
  • the most preferred electron donors are dibutylether or diisoamylether.
  • organic chlorine compound of the present invention it is preferable to use compound of general formula CR' n Cl( 4 - n )(wherein n is an integer between 0 and 3) wherein R' is alkyl radical having carbon number of 1- 12, and most preferred organic chlorine compound is carbon tetrachloride.
  • Silicon compound of the present invention has the general formula of Si(OR) a X4- a » wherein R stands for aliphatic or aromatic hydrocarbon group with carbon number of 1 - 14 or COR' (wherein R' is aliphatic or aromatic hydrocarbon group with carbon number of 1 - 14), X for Cl, Br or I, and a for 0, 1 , 2, 3 or 4.
  • the silicon compound is silicon alkoxyde such as S OC 2 H5V , Si(OC 2 H5)2Cl 2 > Si(OC 2 H 5 )Cl 3 or Si(OC 2 H 5 ) 3 Cl.
  • Organic chlorine compound and silicon compound can be reacted with organic magnesium compound to produce carrier by one of following five methods.
  • the first method is reacting organic magnesium compound with a mixture of silicon compound and organic chlorine compound.
  • the second method is reacting organic magnesium compound and organic chlorine compound, and after certain time, introducing a solution of mixed silicon compound and organic chlorine compound to react with the organic magnesium compound.
  • the third method is mixing silicon compound and organic magnesium compound, and then organic chlorine compound is introduced to react with the organic magnesium compound.
  • the fourth method is introducing silicone compound after the reaction between organic magnesium compound and organic chlorine compound.
  • the last method is introducing silicone compound after the titanium compound treatment.
  • the first method is preferred.
  • the titanium compound used in the present invention has general formula of Ti(OR) a X4-a, wherein R stands for aliphatic or aromatic hydrocarbon group with carbon number of 1 - 14 or COR'(wherein R' is aliphatic or aromatic hydrocarbon group with carbon number of 1 — 14), X for Cl, Br or I, and a for 0, 1 , 2 or 3.
  • Preferred titanium compounds can include TiCl 4 or titanium alkoxychloride such as Ti(OC 3 H 7 )2Cl2, Ti(OC 3 H 7 )Cl 3 , Ti(OC 3 H 7 ) 3 Cl, Ti(OC 4 H 9 )2Cl 2 , Ti(OC 4 H 9 )Cl 3 or Ti ( OC 4 H 9 ) 3 Cl.
  • Organic aluminum compound used herein is organic alkyl aluminum or organic aluminum halogen compound having the formula of AIR' n 3- n - wherein R' stands for alkyl group with 1 - 16, preferably 2- 12 of carbons, X for a halogen compound such as chlorine or bromide and n for an integer or fraction between 0 and 3.
  • organic aluminum compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl aluminum chloride, methyl aluminum chloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquibromide, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, di-n-octyl aluminum iodide, methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride and n-butyl aluminum dichloride.
  • the most preferable organic aluminum compound is selected from the group comprised of dialkyl aluminum chloride and ethyl aluminum sesquichloride.
  • catalyst with particle size of 5- 10// m or 10- 15// m which is useful for ethylene slurry polymerization, and catalyst with particle size of 25- 150 / m which is useful for gas phase ethylene polymerization can be produced.
  • substance containing silicon compound as a component of carrier
  • polyethylene with relatively narrow molecular weight distribution can be obtained compared to the one produced by magnesium carrier which does not contain silicon compound.
  • Narrow molecular weight distribution(MWD) may be characterized by MWD ⁇ 6, measured by gel permeation chromatography, and titanium supported catalyst containing silicon compound of the present invention is appropriate in obtaining polyethylene and polyethylene co-polymer with 2.5 ⁇ MWD ⁇ 4.
  • the catalyst of the present invention can be used in the polymerization of ethylene or co-polymerization of ethylene and alpha-olefin.
  • the catalyst of the present invention can be used together with one or more of organic aluminum compound as a cocatalyst, preferably trialkyl aluminum.
  • Organic aluminum compound which can be used as a cocatalyst has the formula of AlR n X 3 - n , wherein R stands for alkyl radical with carbon number of 1- 12, X for hydrogen atom or halogen atom such as Cl or F, or alkoxy radical with carbon number of 1 — 12, and n for an integer or fraction thereof between 1 — 3.
  • R stands for alkyl radical with carbon number of 1- 12
  • X for hydrogen atom or halogen atom such as Cl or F
  • n for an integer or fraction thereof between 1 — 3.
  • triisobutyl aluminum, triethyl aluminum, trimethyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, ethyl aluminum sesquichloride and diethyl aluminum chloride can be used.
  • Polymerization is carried out by slurry polymerization in the hydrocarbon solvent(such as nucleic acid, heptane) at 50 ⁇ 100 ° C , or by gas phase polymerization at 60 ⁇ 200 ° C under 2 ⁇ 40atm.
  • hydrocarbon solvent such as nucleic acid, heptane
  • gas phase polymerization 60 ⁇ 200 ° C under 2 ⁇ 40atm.
  • hydrogen(5 ⁇ 90 volume%) is used as a control agent of molecular weight of polymer.
  • Propylene, butene- 1 , hexene- 1 , 4- methylpentene- 1 , and other alpha-olefin can be useful in the co- polymerization of ethylene and alpha-olefin.
  • Average particle size of the catalyst is 55// m.
  • Polymerization of ether is carried out in the 2/ of steel reactor with stirrer and temperature control jacket.
  • a hydrocarbon solvent n-hexane(1000m/) is used, and as a cocatalyst 2rnrnol of
  • AKEO 3 is used. Polymerization is carried out at 7.5 atm of ethylene pressure and 4.5atm of hydrogen pressure at 80 ° C for an hour.
  • l lrnole CCI 4 dissolved in the 42m/ of n-hexane, other processes being equal as in the comparative example 1.
  • the result of ethylene polymerization is shown in table 1.
  • the mole ratio of Si/Mg is 0.03 and 3.0m/ of T1CI 4 is used to produce catalyst instead of using mixture of 1.5m/ of TiCl 4 and 3.8m/ of titanium propoxide ⁇ OCsHsV), others being equal as in the example 1.
  • the polymerization process is the same as example 1.
  • Example 3 Using the catalyst obtained in example 2, co-polymerization of ethylene and 1-hexene is carried out.
  • the polymerization process is the same as example 1 except that 150cc of 1-hexane is used before polymerization.
  • co-polymer of ethylene and 1-hexene of density 0.945g/cc is produced.
  • the result of polymerization is shown in table 1.
  • the preparation method of catalyst of the present invention provides highly active catalyst for producing polyethylene resin, which has various particle size depending on the molar ratio of organic silicon compound and magnesium, with narrow particle size distribution.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un procédé d'élaboration de catalyseur pour la polymérisation d'éthylène et la copolymérisation d'éthylène/alpha-oléfine, qui comprend les étapes suivantes: a) élaboration d'un vecteur par réaction entre un composé de magnésium organique MgPh2.nMgCl2.mR2O (Ph=phényle, n=0,37∩0,7, m≥1, R2O=éther), un composé de chlore organique et un composé de silicium à -20∩80 °C, sachant que le rapport molaire entre le composé de chlore organique et Mg est égal ou supérieur à 0,5, et que le rapport molaire entre le composé de silicium et Mg est égal ou supérieur à 0,001; b) traitement du vecteur à base de magnésium avec un composé de titane.
PCT/KR2000/001456 1999-12-14 2000-12-13 Procede d'elaboration de catalyseur supporte pour la polymerisation d'ethylene et la copolymerisation d'ethylene/alpha-olefine WO2001044313A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20293/01A AU2029301A (en) 1999-12-14 2000-12-13 Preparation method of supported catalyst for polymerization of ethylene and co-polymerization of ethylene/alpha-olefin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-1999-0057473A KR100436494B1 (ko) 1999-12-14 1999-12-14 에틸렌 중합 및 에틸렌/알파-올레핀 공중합용 담지촉매의제조방법
KR1999/0057473 1999-12-14

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003044064A1 (fr) * 2001-11-19 2003-05-30 Bp Chemicals Limited Procede de commande de la polymerisation
US6800090B2 (en) 2001-05-14 2004-10-05 Cardiac Dimensions, Inc. Mitral valve therapy device, system and method
EP1749574A1 (fr) * 2004-04-08 2007-02-07 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk Procede de preparation d'un catalyseur et procede de polymerisation d'ethylene et de copolymerisation d'ethylene avec des alpha-olefines
EP1860126A1 (fr) * 2006-05-26 2007-11-28 INEOS Manufacturing Belgium NV Poudre polyoléfinique
CN103772551A (zh) * 2012-10-23 2014-05-07 中国石油化工股份有限公司 一种乙烯聚合反应用催化剂组分及其催化剂
CN104974279A (zh) * 2014-04-11 2015-10-14 中国石油化工股份有限公司 用于乙烯聚合反应的催化剂组分及其催化剂和制备方法
CN105017626B (zh) * 2014-04-15 2018-03-23 中国石化扬子石油化工有限公司 一种乙烯‑α‑烯烃共聚物、其制造方法及其应用

Citations (5)

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JPH01115909A (ja) * 1987-10-28 1989-05-09 Sumitomo Chem Co Ltd オレフィン重合用固体触媒成分
JPH05214025A (ja) * 1991-10-09 1993-08-24 Ecp Enichem Polimeri Sarl オレフィンの重合用触媒
EP0767003A1 (fr) * 1994-06-20 1997-04-09 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk Procede de production d'un catalyseur sous forme de depot pour la polymerisation d'ethylene et la copolymerisation d'ethylene avec des alpha-olefines
KR970027116A (ko) * 1995-11-10 1997-06-24 황선두 에틸렌 중합 및 에틸렌/α-올레핀 공중합용 담지촉매의 제조방법
EP0832136A1 (fr) * 1995-05-12 1998-04-01 Quantum Chemical Corporation Catalyseur a support polymere pour la polymerisation d'olefines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01115909A (ja) * 1987-10-28 1989-05-09 Sumitomo Chem Co Ltd オレフィン重合用固体触媒成分
JPH05214025A (ja) * 1991-10-09 1993-08-24 Ecp Enichem Polimeri Sarl オレフィンの重合用触媒
EP0767003A1 (fr) * 1994-06-20 1997-04-09 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk Procede de production d'un catalyseur sous forme de depot pour la polymerisation d'ethylene et la copolymerisation d'ethylene avec des alpha-olefines
EP0832136A1 (fr) * 1995-05-12 1998-04-01 Quantum Chemical Corporation Catalyseur a support polymere pour la polymerisation d'olefines
KR970027116A (ko) * 1995-11-10 1997-06-24 황선두 에틸렌 중합 및 에틸렌/α-올레핀 공중합용 담지촉매의 제조방법

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800090B2 (en) 2001-05-14 2004-10-05 Cardiac Dimensions, Inc. Mitral valve therapy device, system and method
US7705094B2 (en) 2001-11-19 2010-04-27 Ineos Europe Limited Polymerisation control process
EP1820810A1 (fr) * 2001-11-19 2007-08-22 Ineos Europe Limited Procédé de commande de la polymérisation
WO2003044064A1 (fr) * 2001-11-19 2003-05-30 Bp Chemicals Limited Procede de commande de la polymerisation
EP1749574A1 (fr) * 2004-04-08 2007-02-07 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk Procede de preparation d'un catalyseur et procede de polymerisation d'ethylene et de copolymerisation d'ethylene avec des alpha-olefines
EP1749574A4 (fr) * 2004-04-08 2013-12-25 Dsm Ip Assets Bv Procede de preparation d'un catalyseur et procede de polymerisation d'ethylene et de copolymerisation d'ethylene avec des alpha-olefines
EP1860126A1 (fr) * 2006-05-26 2007-11-28 INEOS Manufacturing Belgium NV Poudre polyoléfinique
WO2007137713A1 (fr) * 2006-05-26 2007-12-06 Ineos Manufacturing Belgium Nv Poudre de polyoléfine
US8124708B2 (en) 2006-05-26 2012-02-28 Ineos Manufacturing Belgium Nv Polyolefin powder
CN103772551A (zh) * 2012-10-23 2014-05-07 中国石油化工股份有限公司 一种乙烯聚合反应用催化剂组分及其催化剂
CN103772551B (zh) * 2012-10-23 2016-08-17 中国石油化工股份有限公司 一种乙烯聚合反应用催化剂组分及其催化剂
CN104974279A (zh) * 2014-04-11 2015-10-14 中国石油化工股份有限公司 用于乙烯聚合反应的催化剂组分及其催化剂和制备方法
CN104974279B (zh) * 2014-04-11 2017-08-25 中国石油化工股份有限公司 用于乙烯聚合反应的催化剂组分及其催化剂和制备方法
CN105017626B (zh) * 2014-04-15 2018-03-23 中国石化扬子石油化工有限公司 一种乙烯‑α‑烯烃共聚物、其制造方法及其应用

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KR20010056057A (ko) 2001-07-04

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