KR900018150A - Preparation method of olefin polymerization catalyst and ethylene copolymer - Google Patents

Abstract

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Description

Preparation method of olefin polymerization catalyst and ethylene copolymer

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1 is a flow chart to facilitate understanding of the present invention.

Claims (25)

(A) The titanium compound represented by the following general formula (II) is reduced with an organic magnesium compound in the presence of an organic porous polymer and an organosilicon compound having a Si—O bond, and the resulting solid product is treated with an ester compound. A solid catalyst component containing trivalent titanium, represented by the following compositional formula (I) obtained by reacting this with a tetrachloride or a mixture of titanium tetrachloride and an electron donating compound, and an olefin containing (B) an organic aluminum compound. Polymerization catalysts. Ng _m Ti (OR) _n X _p [ED] _q (Ⅰ) Wherein R is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen, ED is an electron donating compound, and m, n, p and q are each 1 ≦ m ≦ 51, 0n ≦ 5, 5 ≦ p ≦ 106 and 0.2? Q? 2. Ti (OR ¹ ) _a X _4-a (II) Wherein R ¹ is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom, and a is a number satisfying 0a ≦ 4. The solid catalyst component according to claim 1, wherein R ¹ of the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a is a linear alkyl group having 2 to 18 carbon atoms. The solid catalyst component according to claim 1, wherein _a in the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a is a number satisfying 2a ≦ ₄ . The solid catalyst component according to claim 1, wherein X in the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a is chlorine. The organosilicon compound of claim 1, wherein the organosilicon compound having a general Si—O bond is a general formula Si (OR ³ ) _b R ⁴ _4-b , R ⁵ (R ⁶ ₂ SiO) _c SiR ⁷ or (R ⁸ ₂ SiO) ₄ (wherein R ³ is a hydrocarbon group of 1 to 20 carbon atoms, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrocarbon group or hydrogen atom of 1 to 20 carbon atoms, b is 0 ≦ b A solid catalyst component which is an organosilicon compound represented by a number satisfying? The solid catalyst component according to claim 5, wherein _b in the organosilicon compound represented by the general formula Si (OR ³ ) _b R ⁴ _4-b satisfies 1 ≦ b ≦ ₄ . The Grignard compound according to claim 1, wherein the organic magnesium compound is represented by general formula R ⁹ MgX, wherein R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms and X is a halogen atom, or a general formula R ¹⁰ R ^A solid catalyst component which is a diaryl magnesium compound or a dialkyl magnesium compound represented by ¹¹ Mg, wherein R ¹⁰ and R ¹¹ are each a hydrocarbon group having 1 to 20 carbon atoms. The solid catalyst component of claim 1 wherein the organic porous chamber polymer is polystyrene, styrene-divinylbenzene copolymer or polyvinyl chloride. The solid catalyst component of claim 8, wherein the organic porous polymer has a pore volume of at least 0.1 cc / g and an average particle diameter of 5 to 1,000 μm at a pore radius of 100 to 5000 angstroms. The solid catalyst component according to claim 1, wherein the ester compound is an aliphatic carboxylic acid ester, an olefinic carboxylic acid ester, an alicyclic carboxylic acid ester or an aromatic carboxylic acid ester. The solid catalyst component of claim 1 wherein the electron donating compound is an ester compound, ether compound or ketone compound. 12. The solid catalyst component of claim 11 wherein the ester compound is an aliphatic carboxylic acid ester, an olefinic carboxylic acid ester, an alicyclic carboxylic acid ester or an aromatic carboxylic acid ester. The solid catalyst component according to claim 1, wherein the amount of organosilicon compound used is 1 to 50, based on the atomic ratio (Si / Ti) of silicon atoms to titanium atoms. The solid catalyst component according to claim 1, wherein the amount of the organic magnesium compound used is 0.1 to 10 based on the atomic ratio (Si + Ti / Mg) of titanium and silicon atoms to magnesium atoms. The solid catalyst component of claim 1 wherein the reduction reaction is carried out at a temperature of -50 to 70 ° C. The solid catalyst component of claim 1 wherein the amount of organic porous polymer used is from 20 to 90% by weight relative to the proportion in the solid product. The solid catalyst component according to claim 1, wherein the amount of ester compound used is 0.01 to 1.0 mol per mol of magnesium atoms in the solid product and 0.1 to 50 mol per mol of titanium atoms in the solid product. The solid catalyst component according to claim 1, wherein the usage amount of titanium tetrachloride is 1 to 1000 moles per mole of titanium atoms in the solid product. The organoaluminum compound of claim 1, wherein the organoaluminum compound has at least one A 1 -C bond in the molecule, wherein the general aluminum, R ¹² _r A1Y ₃ -or R ¹³ R ¹⁴ A1-O-A1R ¹⁵ R ¹⁶ , wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each a hydrocarbon group having 1 to 8 carbon atoms, Y is a halogen atom, a hydrogen atom or an alkoxy group, and r is a number satisfying 2 ≦ r ≦ 3). An olefin polymerization catalyst which is a compound. 20. The olefin polymerization catalyst of claim 19 wherein the organoaluminum compound is a mixture of trialkylaluminum, trialkylaluminum and dialkylaluminum halides, or alkylalutoic acid. The olefin polymerization catalyst according to claim 1, wherein the amount of organoaluminum compound used is 1 to 1000 moles per mole of titanium atoms in the solid product. A method for producing an ethylene copolymer, characterized in that the ethylene polymerization catalyst according to claim 1 is copolymerized with at least one alpha-olefin and ethylene having 3 or more carbon atoms. The method of claim 22, wherein said method is carried out at a temperature below the melting point temperature of the polymer to produce an ethylene copolymer. 23. The process of claim 22, wherein the process is carried out at a pressure ranging from atmospheric pressure to 40 kg / cm < 3 > and at a temperature of from 20 to 100 < 0 > C. 23. The ethylene copolymer of claim 22, wherein the alpha-olefin having at least 3 carbon atoms is propene, butene-1, pentene-1, hexene-1, 3-methyl-pentene-1 or 4-fetylpentene-1. How to. ※ Note: The disclosure is based on the initial application.