Process for polymerization or copolymerization of ethylene
Provided is a process for polymerization and copolymerization of ethylene, specifically comprising carrying out polymerization or copolymerization ethylene in the presence of (a) a solid complex titanium catalyst which is produced by the process comprising: (i) preparing a magnesium compound solution by contacting a halogenated magnesium compound and an alcohol for allowing a reaction; (ii) reacting the resulted magnesium compound solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group; (iii) reacting the resulted solution with a mixture of a titanium compound and a silicon compound to obtain a solid titanium catalyst component; (iv) washing the resulted solid titanium catalyst component with a halogenated saturated hydrocarbon compound; and (v) further reacting the washed solid titanium catalyst component with a titanium compound to obtain a solid complex titanium catalyst, and (b) an organometallic compound from Group II or III of Periodic table of elements. According to the present invention, it is possible to provide a process for polymerization or copolymerization of ethylene in which the catalyst activity is improved and a polymer of high bulk density is provided, with the use of a catalyst prepared by a simple process.
1. A process for polymerizing or copolymerizing ethylene comprising carrying out polymerization or copolymerization of ethylene in the presence of (a) and (b):
(a) a solid complex titanium catalyst which is produced by the process comprising:
(i) preparing a magnesium compound solution by contacting a halogenated magnesium compound and an alcohol;
(ii) reacting the resulted magnesium compound solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group;
(iii) reacting the resulted solution with a mixture of a titanium compound and a silicon compound to obtain a solid titanium catalyst component;
(iv) washing the resulted solid titanium catalyst component with a halogenated saturated hydrocarbon compound; and
(v) further reacting the washed solid titanium catalyst component with a titanium compound to obtain a solid complex titanium catalyst, and
(b) an organometallic compound from Group II or III of Periodic table of elements.
2. The process for polymerizing or copolymerizing ethylene according to claim 1 , wherein the ester compound having at least one hydroxyl group is selected from the group consisting of unsaturated fatty acid esters having at least one hydroxyl group, aliphatic monoesters or polyesters having at least one hydroxyl group, aromatic esters having at least one hydroxyl group, and alicyclic esters having at least one hydroxyl group; and the silicon compound having at least one alkoxy group is at least one selected from alkoxy silane compounds represented by the general formula of R n (OR) 4-n , wherein R is a hydrocarbon group having C1-12, and n is an integer of 0-3.
3. The process for polymerizing or copolymerizing ethylene according to claim 1 , wherein the titanium compound and the silicon compound are represented by each general formula of T(OR) a X 4-a , in which R is a hydrocarbon group; X is a halogen atom; and a is an integer of 0-4, and R n SiC 4-n , in which R is a hydrogen atom, an alkyl group having C1-10, alkoxy, haloalkyl, aryl group, or halosilyl group having C1-8 or halosilylalkyl group; and n is an integer of 0-3.
4. The process for polymerizing or copolymerizing ethylene according to claim 3 , wherein the titanium compound is at least one selected from the group consisting of TiCl 4 , TiBr 4 , TiI 4 , Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(OC 2 H 5 )Br 3 , Ti(O(i-C 4 H 9 ))Br 3 , Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 , Ti(O(i-C 4 H 9 )) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Br 2 , Ti(OCH 3 ) 4 , Ti(OC 2 H 5 ) 4 and Ti(OC 4 H 9 ) 4 .
5. The process for polymerizing or copolymerizing ethylene according to claim 1 , wherein the halogenated saturated hydrocarbon compound is at least one selected from the group consisting of ethyldichloride, chloroform, ter-butyl chloride, tetrachloromethane, ethylbromide, tert-butyliodide, n-butylbromide, n-butyliodide and n-butylfluoride.
6. The process for polymerizing or copolymerizing ethylene according to claim 1 , wherein the washing process using a halogenated saturated hydrocarbon compound in the step (iv) is repeated once to 5 times.