Preparation method of a catalyst component for olefin polymerization

Patent metadata

Field	Value
Publication number	US-10174141-B2
Application number	US-201515307209-A
Country	US
Kind code	B2
Filing date	Apr 29, 2015
Priority date	Apr 29, 2014
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

The present invention provides a preparation method of a catalyst component for olefin polymerization, comprising firstly dissolving an anhydrous magnesium halide into a mixed solvent which comprises an oxygen-containing organic titanium compound, an organic epoxy compound, a hydroxy-containing compound, and an inert solvent, and does not comprise a phosphate compound, so as to form a magnesium halide solution; then mixing the magnesium halide solution with a halogen-containing compound to precipitate a solid, so as to obtain the catalyst component, wherein the halogen-containing compound comprises at least one selected from a group consisting of halogen and titanium-containing compounds, halogenated organic hydrocarbon compounds, acyl halide compounds, halogen and phosphorus-containing compounds, halogen and boron-containing compounds, halogenated organic aluminum compounds, and halogen and silicon-containing compounds. The catalyst component prepared by the present invention has better particle morphology, and a good hydrogen response, and thus is favorable to use of the catalyst in a slurry or gas polymerization process device.

First claim

The invention claimed is:

1. A catalyst component for olefin polymerization, which is obtained by mixing a magnesium halide solution containing an organic epoxy compound with a halogen-containing compound to precipitate a solid;
wherein, the organic epoxy compound is a three membered epoxy compound as shown in Formula I,

wherein, R 2 are R 3 are independently selected from H, or C 1 -C 10 hydrocarbyl or halogenated hydrocarbyl, and can be a saturated or unsaturated straight, branched, or cyclic chain; or the organic epoxy compound is a 4-8 membered epoxy compound;
the halogen-containing compound comprises at least one selected from the group consisting of acyl halide compounds and halogen and silicon-containing compounds;
the halogen and silicon-containing compound contains at least one silicon-halogen bond; and
the magnesium halide solution is formed by dissolving an anhydrous magnesium halide into a mixed solvent which comprises an oxygen-containing organic titanium compound, the organic epoxy compound, a hydroxy-containing compound, and an inert solvent, and does not comprise a phosphate or a phosphite compound.

2. The catalyst component according to claim 1 , wherein the magnesium halide solution is formed by dissolving the anhydrous magnesium halide into a mixed solvent which is comprised of the oxygen-containing organic titanium compound, the organic epoxy compound, the hydroxy-containing compound, and the inert solvent.

3. The catalyst component according to claim 1 , wherein the magnesium halide is as shown in Formula MgX 2 , in which X is halogen; the oxygen-containing organic titanium compound is as shown in Formula Ti(OR 1 ) n X 4-n , in which R 1 is C 1 -C 20 hydrocarbyl, and can be a saturated or unsaturated straight, branched, or cyclic chain, 0<n≤4, and X is halogen; the hydroxy-containing compound is as shown in Formula HOR 4 , in which R 4 is C 1 -C 20 hydrocarbyl, and can be a saturated or unsaturated straight, branched, or cyclic chain; the inert solvent is C 3 -C 100 aliphatic hydrocarbon or halogenated aliphatic hydrocarbon, aromatic hydrocarbon or halogenated aromatic hydrocarbon, and can be a saturated or unsaturated straight, branched, or cyclic chain.

4. The catalyst component according to claim 1 , wherein the magnesium halide is selected from the group consisting of magnesium chloride, magnesium bromide, magnesium iodide and mixtures thereof; the oxygen-containing organic titanium compound is selected from the group consisting of titanate compounds and mixtures thereof; the hydroxy-containing compound is selected from the group consisting of aliphatic alcohols, aromatic alcohols, and phenols; the inert solvent is selected from the group consisting of benzene, toluene, xylene, n-butane, isobutane, isopentane, pentane, n-hexane, cyclohexane, heptane, octane, decane, 1,2-dichloroethane, chlorobenzene and mixtures thereof.

5. The catalyst component according to claim 1 , wherein calculated based on per molar magnesium halide, the oxygen-containing organic titanium compound is 0.01-2.0 mol; the organic epoxy compound is 0.01-10 mol; the hydroxy-containing compound is 0.01-20 mol; the halogen-containing compound is 0.1-100 mol.

6. The catalyst component according to claim 1 , wherein the organic epoxy compound is one or more selected from the group consisting of ethylene oxide, propylene oxide, butylenes oxide, butadiene oxide, butadiene dioxide, epoxy chloropropane, methyl glycidyl ether, diglycidyl ether, and terahydrofuran.

7. The catalyst component according to claim 1 , wherein the acyl halide compound is a compound as shown in Formula R 5 COX, in which R 5 is C 1 -C 20 hydrocarbyl, or hydrogen, and can be a saturated or unsaturated straight, branched, or cyclic chain, and X is halogen.

8. The catalyst component according to claim 7 , wherein the acyl halide compound comprises at least one selected from the group consisting of acyl fluoride compound, acyl chloride compound, acyl bromide compound, and acyl iodide compound.

9. The catalyst component according to claim 1 , wherein the halogen and silicon-containing compound is a compound as shown in Formula (R 5 O) q SiR 6 n X 4-n-q , in which R 5 and R 6 are independently selected from C 1 -C 20 hydrocarbyl or halogenated hydrocarbyl, and can be saturated or unsaturated straight, branched, or cyclic chain; each of q and n is 0 or a positive number, and 0≤q+n≤3; X is halogen.

10. The catalyst component according to claim 9 , wherein the halogen and silicon-containing compound is at least one selected from the group consisting of silicon tetrachloride, silicon tetrabromide, ethoxysilicon trichloride, phenylsilicon trichloride, methylsilicon trichloride, ethylsilicon trichloride, diethoxysilicon dichloride, methylmethoxysilicon dichloride, and methylphenoxysilicon dichloride.

11. A preparation method of the catalyst component according to claim 1 , comprising firstly dissolving an anhydrous magnesium halide into a mixed solvent which comprises an oxygen-containing organic titanium compound, an organic epoxy compound, a hydroxy-containing compound, and an inert solvent, and does not comprise a phosphate or a phosphite compound, so as to form a magnesium halide solution; then mixing the magnesium halide solution with a halogen-containing compound to precipitate a solid, so as to obtain the catalyst component;
wherein the organic epoxy compound is a three membered epoxy compound as shown in Formula I,

wherein, R 2 are Ware independently selected from H, or C 1 -C 10 hydrocarbyl or halogenated hydrocarbyl, and can be saturated or unsaturated straight, branched, or cyclic chain; or the organic epoxy compound is a 4-8 membered epoxy compound;
the halogen-containing compound comprises at least one selected from the group consisting of acyl halide compounds and halogen and silicon-containing compounds.

12. The method according to claim 11 , wherein the magnesium halide solution is formed by dissolving an anhydrous magnesium halide into a mixed solvent consisting of an oxygen-containing organic titanium compound, an organic epoxy compound, hydroxy-containing compound, and an inert solvent.

13. A catalyst for olefin polymerization, comprising a reaction product of the following components:
(a) the catalyst component according to claim 1 ;
(b) at least one organic aluminum compound as shown in Formula AlR m X 3-m , in which R is hydrogen or C 1 -C 20 hydrocarbyl, X is halogen, and m is 0<m≤3.

14. A magnesium halide solution system used for the preparation process of a catalyst component for olefin polymerization, comprising an oxygen-containing organic titanium compound, an organic epoxy compound, a hydroxy-containing compound, and an inert solvent, wherein the magnesium halide solution system does not comprise a phosphate compound or a phosphite, further wherein the organic epoxy compound is a three membered epoxy compound as shown in Formula I,

wherein, R 2 are R 3 are independently selected from H, or C 1 -C 10 hydrocarbyl or halogenated hydrocarbyl, and can be saturated or unsaturated straight, branched, or cyclic chain; or the organic epoxy compound is a 4-8 membered epoxy compound.

15. The magnesium halide solution system according to claim 14 , wherein the magnesium halide s

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp
• China Petroleum & Chemical Corporation Beijing Res Institute Of Chemical Industry China Petroleum &

Inventors

• Wang Shibo
• Zhou Junling
• Liu Dongbing
• Zhang Lei
• Lv Xinping
• Mao Bingquan
• Liu Zhenjie
• Zhou Xin
• Zhang Changli
• Xing Baoquan

Classifications

• C08F2500/18

  Bulk density · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F4/651

  Pretreating with non-metals or metal-free compounds · CPC title

• C08F4/6543

  halides of magnesium · CPC title

• C08F4/6574

  and magnesium or compounds thereof · CPC title