Preparation method of a catalyst component for olefin polymerization

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.

Claims

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, ##STR00004## wherein, R.sup.2 are R.sup.3 are independently selected from H, or C.sub.1-C.sub.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.sub.2, in which X is halogen; the oxygen-containing organic titanium compound is as shown in Formula Ti(OR.sup.1).sub.nX.sub.4-n, in which R.sup.1 is C.sub.1-C.sub.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.sup.4, in which R.sup.4 is C.sub.1-C.sub.20 hydrocarbyl, and can be a saturated or unsaturated straight, branched, or cyclic chain; the inert solvent is C.sub.3-C.sub.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.sup.5COX, in which R.sup.5 is C.sub.1-C.sub.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.sup.5O).sub.qSiR.sup.6.sub.nX.sub.4-n-q, in which R.sup.5 and R.sup.6 are independently selected from C.sub.1-C.sub.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, ##STR00005## wherein, R.sup.2 are Ware independently selected from H, or C.sub.1-C.sub.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.sub.mX.sub.3-m, in which R is hydrogen or C.sub.1-C.sub.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, ##STR00006## wherein, R.sup.2 are R.sup.3 are independently selected from H, or C.sub.1-C.sub.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 solution system is a mixed solvent which is comprised of an oxygen-containing organic titanium compound, an organic epoxy compound, a hydroxy-containing compound, and an inert solvent.

16. The catalyst component according to claim 3, wherein the inert solvent is a C.sub.4-C.sub.20 hydrocarbon.

17. The catalyst component according to claim 4, wherein the oxygen-containing organic titanium compound is selected from the group consisting of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraisooctyl titanate.

18. The catalyst component according to claim 4, wherein the hydroxy-containing compound is selected from the group consisting of methanol, ethanol, isopropanol, n-butanol, n-hexanol, isooctanol, benzyl alcohol, and phenethyl alcohol.

19. The catalyst component according to claim 5, wherein calculated based on per molar magnesium halide, the oxygen-containing organic titanium compound is 0.1-1.5 mol; the organic epoxy compound is 0.1-6.5 mol; the hydroxy-containing compound is 0.1-15 mol; the halogen-containing compound is 0.5-50 mol.

20. The catalyst component according to claim 8, wherein the acyl halide compound is an acyl chloride compound.

21. The catalyst component according to claim 10, wherein the halogen and silicon-containing compound is at least one selected from the group consisting of silicon tetrachloride, silicon tetrabromide, ethoxysilicon trichloride, and phenylsilicon trichloride.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Measuring Methods

(2) 1. Particle size distribution of carriers and catalysts; measured by MASTERSIZE particle size analyzer with n-hexane as dispersant, and the measuring scope being 0.02-2000 ?m.

(3) 2. Weight percentage of metals (mainly titanium and magnesium) in a catalyst: measured using an ICP plasma spectrometer.

(4) 3. Melt index; measured based on ASTMD1238 standard.

(5) 4. Bulk density: measured based on DIN-53194 standard.

(6) The embodiments below are provided for illustrating, rather than restricting the present invention.

EXAMPLES

(7) In the following Examples 1 to 5, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with a halogen and titanium-containing compound to precipitate a solid, thus obtaining a catalyst component.

Example 1

(8) Preparation of a Catalyst Component:

(9) 2.4 g of anhydrous magnesium chloride was measured, followed by addition of 8.8 mL of tetrabutyl titanate, 2.0 mL of epoxy chloropropane, 2.2 mL of anhydrous ethanol, and 50 mL of methylbenzene. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of methylbenzene was again added. The solution was cooled to ?20? C., followed by slow drop wise addition of 30 mL of titanium tetrachloride from a burette. After that, the solution was kept at ?20? C. and reacted for 0.5 hour, then heated to 50? C. and reacted for 4 hours, and finally heated to 90? C. and reacted for 3 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, and washed for four times with 50 mL of methylbenzene each time, and washed twice with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a solid white free-flowing power. The solid white free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 3.48 ?m. Elemental Analysis: Ti: 9.82% (by weight), Mg: 15.42% (by weight).

(10) Evaluation of Catalyst:

(11) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 80? C. followed by addition of 0.18 MPa of hydrogen gas. The total pressure of the system was maintained at 0.73 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI.sub.2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 1.

Example 2

(12) Preparation of a Catalyst Component:

(13) Conditions used in the present example were the same as those used in example 1, except that the step the solution was cooled to ?20? C. in example 1 was amended into the solution was cooled to 0? C., the step the solution was kept at ?20? C. and reacted for 0.5 hour was amended into the solution was kept at 0? C. and reacted for 0.5 hour, and the step followed by slow drop wise addition of 30 mL of titanium tetrachloride from a burette was amended into followed by slow drop wise addition of 15 mL of titanium tetrachloride from a burette. The average particle size of the obtained catalyst was 8.65 ?m. Elemental Analysis (ICP): Ti: 6.75% (by weight), Mg: 19.71% (by weight).

(14) Evaluation of Catalyst:

(15) Slurry polymerization conditions of the catalyst were the same as those in example 1. Results were shown in Table 1.

Example 3

(16) Preparation of a Catalyst Component:

(17) Conditions used in the present example were the same as those used in example 1, except that 2.2 mL of anhydrous ethanol in example 1 was changed into 11.8 mL of isooctanol. The average particle size of the obtained catalyst was 3.92 ?m. Elemental Analysis (ICP): Ti: 27.61% (by weight), Mg: 10.10% (by weight).

(18) Evaluation of Catalyst:

(19) Slurry polymerization conditions of the catalyst were the same as those in example 1. Results were shown in Table 1.

Example 4

(20) Preparation of a Catalyst Component:

(21) Conditions used in the present example were the same as those used in example 1, except that 2.2 mL of anhydrous ethanol in example 1 was changed into 6.9 mL of n-butyl alcohol. The average particle size of the obtained catalyst was 2.82 ?m. Elemental Analysis (ICP): Ti: 6.69% (by weight), Mg: 19.8% (by weight).

(22) Evaluation of Catalyst:

(23) Slurry polymerization conditions of the catalyst were the same as those in example 1. Results were shown in Table 1.

Example 5

(24) Preparation of a Catalyst Component:

(25) Conditions used in the present example were the same as those used in example 1, except that 8.8 mL of tetrabutyl titanate in example 1 was changed into 5.5 mL of tetraethyl titanate, and 2.0 mL of epoxy chloropropane was changed into 2.1 mL of tetrahydrofuran. The average particle size of the obtained catalyst was 7.64 ?m. Elemental Analysis (ICP): Ti: 12.22% (by weight), Mg: 16.06% (by weight).

(26) Evaluation of Catalyst:

(27) Slurry polymerization conditions of the catalyst were the same as those in example 1. Results were shown in Table 1.

(28) TABLE-US-00001 TABLE 1 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 1 41.3 0.41 0.34 Example 2 23.8 0.62 0.33 Example 3 13.6 0.18 0.32 Example 4 37.3 0.29 0.33 Example 5 40.4 0.72 0.32

(29) In the following Examples 6 to 9, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with a halogenated organic hydrocarbon compound to precipitate a solid, thus obtaining a catalyst component.

Example 6

(30) Preparation of a catalyst component;

(31) 2.4 g of anhydrous magnesium chloride was measured, followed by addition of 8.8 mL of tetrabutyl titanate, 2.0 mL of epoxy chloropropane, 2.2 mL of anhydrous ethanol, and 50 mL of methylbenzene. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of methylbenzene was again added. The solution was cooled to 0? C., followed by slow drop wise addition of 25 mL of chloro-t-butane, from a burette. After that, the solution was kept at 0? C. and reacted for 0.5 hour, then heated to 50? C. and reacted for 3 hours, and finally heated to 90? C. and reacted for 2 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, washed for four times with 50 mL of methylbenzene each time, and washed twice with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a solid white free-flowing power. The solid white free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 33.72 ?m. Elemental Analysis: Ti: 15.24% (by weight), Mg: 16.74% (by weight).

(32) Evaluation of Catalyst:

(33) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 85? C., followed by addition of 0.18 MPa of hydrogen gas. The total pressure of the system was maintained at 1.03 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI.sub.2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 2.

Example 7

(34) Preparation of a Catalyst Component:

(35) Conditions used in the present example were the same as those used in example 6, except that the step the solution was cooled to 0? C. in example 6 was amended into the solution was cooled to 45? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 45? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 24.52 ?m. Elemental Analysis (ICP): Ti: 8.33% (by weight), Mg: 14.17% (by weight).

(36) Evaluation of Catalyst:

(37) Slurry polymerization conditions of the catalyst were the same as those in example 6. Results were shown in Table 2.

Example 8

(38) Preparation of a Catalyst Component:

(39) Conditions used in the present example were the same as those used in example 6, except that 8.8 mL of tetrabutyl titanate in example 6 was changed into 5.5 mL of tetraethyl titanate. The average particle size of the obtained catalyst was 41.29 ?m. Elemental Analysis (ICP): Ti: 6.53% (by weight), Mg: 12.20% (by weight).

(40) Evaluation of Catalyst:

(41) Slurry polymerization conditions of the catalyst were the same as those in example 6. Results were shown in Table 2.

Example 9

(42) Preparation of a Catalyst Component:

(43) Conditions used in the present example were the same as those used in example 6, except that 2.2 ml, of anhydrous ethanol in example 6 was changed into 6.9 mL of n-butyl alcohol. The average particle size of the obtained catalyst was 28.07 ?m. Elemental Analysis (ICP): Ti: 4.88% (by weight), Mg: 13.59% (by weight).

(44) Evaluation of Catalyst:

(45) Slurry polymerization conditions of the catalyst were the same as those in example 6. Results were shown in Table 2.

(46) TABLE-US-00002 TABLE 2 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 6 3.65 0.68 0.32 Example 7 5.63 0.81 0.34 Example 8 3.08 0.52 0.30 Example 9 2.67 0.93 0.31

(47) In the following Examples 10 to 13, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with an acyl chloride compound to precipitate a solid, thus obtaining a catalyst component.

Example 10

(48) Preparation of a Catalyst Component:

(49) 2.4 g of anhydrous magnesium chloride was measured, followed by addition of 8.8 mL of tetrabutyl titanate, 2.0 mL of epoxy chloropropane, 2.2 mL of anhydrous ethanol, and 50 mL of methylbenzene. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of methylbenzene was again added. The solution was cooled to 0? C., followed by slow drop wise addition of 27 mL of benzoyl chloride from a burette. After that, the solution was kept at 0? C. and reacted for 0.5 hour, then heated to 50? C. and reacted for 3 hours, and finally heated to 90? C. and reacted for 2 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, washed for four times with 50 mL of methylbenzene each time, and washed twice with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a solid white free-flowing power. The solid white free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 35.63 ?m. Elemental Analysis: Ti: 16.37% (by weight), Mg: 13.16% (by weight).

(50) Evaluation of Catalyst:

(51) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 85? C., followed by addition of 0.18 MPa of hydrogen gas. The total pressure of the system was maintained at 1.03 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI.sub.2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 3.

Example 11

(52) Preparation of a Catalyst Component:

(53) Conditions used in the present example were the same as those used in example 10, except that the step the solution was cooled to 0? C. in example 10 was amended into the solution was cooled to 45? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 45? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 23.54 ?m. Elemental Analysis (ICP): Ti: 9.86% (by weight), Mg: 18.25% (by weight).

(54) Evaluation of Catalyst:

(55) Slurry polymerization conditions of the catalyst were the same as those in example 10. Results were shown in Table 3.

Example 12

(56) Preparation of a Catalyst Component;

(57) Conditions used in the present example were the same as those used in example 10, except that 27 mL of benzoyl chloride in example 10 was changed into 14 mL of benzoyl chloride. The average particle size of the obtained catalyst was 38.18 ?m. Elemental Analysis (ICP): Ti: 15.27% (by weight), Mg: 12.47% (by weight).

(58) Evaluation of Catalyst:

(59) Slurry polymerization conditions of the catalyst were the same as those in example 10. Results were shown in Table 3.

Example 13

(60) Preparation of a Catalyst Component:

(61) Conditions used in the present example were the same as those used in example 10, except that 2.2 mL of anhydrous ethanol in example 10 was changed into 6.9 mL of n-butyl alcohol. The average particle size of the obtained catalyst was 42.45 ?m. Elemental Analysis (ICP): Ti: 11.15% (by weight), Mg: 13.62% (by weight).

(62) Evaluation of Catalyst:

(63) Slurry polymerization conditions of the catalyst were the same as those in example 10. Results were shown in Table 3.

(64) TABLE-US-00003 TABLE 3 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 10 6.72 1.24 0.33 Example 11 8.26 0.83 0.35 Example 12 4.13 1.34 0.32 Example 13 5.21 0.96 0.34

(65) In the following Examples 14 to 17, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with a halogen and phosphorus-containing compound to precipitate a solid, thus obtaining a catalyst component.

Example 14

(66) Preparation of a Catalyst Component:

(67) 2.4 g of anhydrous magnesium chloride was measured, followed by addition of 8.8 mL, of tetrabutyl titanate, 2.0 mL of epoxy chloropropane, 2.2 mL of anhydrous ethanol, and 50 mL of methylbenzene. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of methylbenzene was again added. The solution was cooled to 0? C., followed by slow drop wise addition of 35 mL of phosphorus trichloride from a burette. After that, the solution was kept at 0? C. and reacted for 0.5 hour, then heated to 50? C. and reacted for 3 hours, and finally heated to 90? C. and reacted for 2 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, washed for four times with 50 mL of methylbenzene each time, and washed twice with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a solid white free-flowing power. The solid white free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 16.7 ?m. Elemental Analysis: Ti: 0.54% (by weight), Mg: 26.39% (by weight).

(68) Evaluation of Catalyst:

(69) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 80? C., followed by addition of 0.18 MPa of hydrogen. The total pressure of the system was maintained at 0.73 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 4.

Example 15

(70) Preparation of a Catalyst Component:

(71) Conditions used in the present example were the same as those used in example 14, except that the step the solution was cooled to 0? C. in example 14 was amended into the solution was cooled to 45? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 45? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 33.56 ?m. Elemental Analysis (ICP): Ti: 0.67% (by weight), Mg: 25.34% (by weight).

(72) Evaluation of Catalyst:

(73) Slurry polymerization conditions of the catalyst were the same as those in example 14. Results were shown in Table 4.

Example 16

(74) Preparation of a Catalyst Component:

(75) Conditions used in the present example were the same as those used in example 14, except that 8.8 mL of tetrabutyl titanate in example 14 was changed into 5.5 mL of tetraethyl titanate. The average particle size of the obtained catalyst was 21.46 ?m. Elemental Analysis (ICP): Ti: 0.86% (by weight), Mg: 20.5% (by weight).

(76) Evaluation of Catalyst:

(77) Slurry polymerization conditions of the catalyst were the same as those in example 14. Results were shown in Table 4.

Example 17

(78) Preparation of a Catalyst Component:

(79) Conditions used in the present example were the same as those used in example 14, except that 2.2 mL of anhydrous ethanol in example 14 was changed into 4.6 mL of n-butyl alcohol, and that the step the solution was cooled to 0? C. in example 14 was amended into the solution was cooled to 45? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 45? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 26.35 ?m. Elemental Analysis (ICP): Ti: 0.97% (by weight), Mg: 28.82% (by weight).

(80) Evaluation of Catalyst:

(81) Slurry polymerization conditions of the catalyst were the same as those in example 14. Results were shown in Table 4.

(82) TABLE-US-00004 TABLE 4 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 14 6.2 0.76 0.35 Example 15 4.7 0.62 0.34 Example 16 3.9 0.57 0.34 Example 17 5.7 0.61 0.36

(83) In the following Examples 18 to 21, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with a halogen and boron-containing compound to precipitate a solid, thus obtaining a catalyst component.

Example 18

(84) Preparation of a Catalyst Component:

(85) 2.4 g of anhydrous magnesium chloride was measured, followed by addition of 8.8 mL of tetrabutyl titanate, 2.0 mL of epoxy chloropropane, 2.2 mL of anhydrous ethanol, and 50 mL of methylbenzene. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of methylbenzene was again added. The solution was cooled to 0? C., followed by slow drop wise addition of 50 mL of hexane solution of boron trichloride (1M) from a burette. After that, the solution was kept at 0? C. and reacted for 0.5 hour, then heated to 50? C. and reacted for 3 hours, and finally heated to 65? C. and reacted for 2 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, washed for four times with 50 mL of methylbenzene each time, and washed twice with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a solid white free-flowing power. The solid white free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 25.57 ?m. Elemental Analysis: Ti: 1.36% (by weight), Mg: 27.86% (by weight).

(86) Evaluation of Catalyst:

(87) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 80? C., followed by addition of 0.18 MPa of hydrogen gas. The total pressure of the system was maintained at 0.73 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 5.

Example 19

(88) Preparation of a Catalyst Component:

(89) Conditions used in the present example were the same as those used in example 18, except that the step the solution was cooled to 0? C. in example 18 was amended into the solution was cooled to 30? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 30? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 18.47 ?m. Elemental Analysis (ICP): 1.54% (by weight), Mg: 27.95% (by weight).

(90) Evaluation of Catalyst:

(91) Slurry polymerization conditions of the catalyst were the same as those in example 18. Results were shown in Table 5.

Example 20

(92) Preparation of a Catalyst Component:

(93) Conditions used in the present example were the same as those used in example 18, except that 2.0 mL of epoxy chloropropane in example 18 was changed into 2.1 mL of tetrahydrofuran. The average particle size of the obtained catalyst was 31.29 ?m. Elemental Analysis (ICP): Ti: 0.92% (by weight), Mg: 22.16% (by weight).

(94) Evaluation of Catalyst:

(95) Slurry polymerization conditions of the catalyst were the same as those in example 18 Results were shown in Table 5.

Example 21

(96) Preparation of a Catalyst Component:

(97) Conditions used in the present example were the same as those used in example 18, except that 2.2 mL of anhydrous ethanol in example 18 was changed into 4.6 mL of n-butyl alcohol. The average particle size of the obtained catalyst was 20.85 ?m. Elemental Analysis (ICP): Ti: 0.76% (by weight), Mg: 21.65% (by weight).

(98) Evaluation of Catalyst:

(99) Slurry polymerization conditions of the catalyst were the same as those in example 18. Results were shown in Table 5.

(100) TABLE-US-00005 TABLE 5 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 18 22.1 0.41 0.33 Example 19 24.8 0.35 0.34 Example 20 18.6 0.53 0.36 Example 21 16.5 0.73 0.34

(101) In the following Examples 22 to 25, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with a halogenated organic aluminium compound to precipitate a solid, thus obtaining a catalyst component.

Example 22

(102) Preparation of a Catalyst Component:

(103) 1.2 g of anhydrous magnesium chloride was measured, followed by addition of 4.4 mL of tetrabutyl titanate, 1.0 mL of epoxy chloropropane, 1.1 mL of anhydrous ethanol, and 50 mL of hexane. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of hexane was again added. The solution was cooled to 0? C., followed by slow drop wise addition of 18 mL of hexane solution of ethyl aluminium dichloride (3M) from a burette. After that, the solution was kept at 0? C. and reacted for 0.5 hour, and then heated to 65? C. and reacted for 3 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, and washed for four times with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a free-flowing power. The free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 15.68 ?m. Elemental Analysis: Ti: 11.48% (by weight), Mg: 13.78% (by weight).

(104) Evaluation of Catalyst:

(105) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 90? C., followed by addition of 0.4 MPa of hydrogen. The total pressure of the system was maintained at 1.0 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 6.

Example 23

(106) Preparation of a Catalyst Component:

(107) Conditions used in the present example were the same as those used in example 22, except that the step the solution was cooled to 0? C. in example 22 was amended into the solution was cooled to 45? C., and the step the solution was kept at 0? C., and reacted for 0.5 hour was amended into the solution was kept at 45? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 14.77 ?m. Elemental Analysis (ICP); Ti: 7.64% (by weight), Mg; 16.06% (by weight).

(108) Evaluation of Catalyst:

(109) Slurry polymerization conditions of the catalyst were the same as those in is example 22. Results were shown in Table 6.

Example 24

(110) Preparation of a Catalyst Component:

(111) Conditions used in the present example were the same as those used in example 22, except that 4.4 mL of tetrabutyl titanate in example 22 was changed into 2.8 mL of tetraethyl titanate. The average particle size of the obtained catalyst was 21.64 ?m. Elemental Analysis (ICP); Ti: 10.92% (by weight), Mg: 16.33% (by weight).

(112) Evaluation of Catalyst:

(113) Slurry polymerization conditions of the catalyst were the same as those in example 22. Results were shown in Table 6.

Example 25

(114) Preparation of a Catalyst Component:

(115) Conditions used in the present example were the same as those used in example 22, except that 1.1 mL of anhydrous ethanol in example 22 was changed into 2.3 mL of n-butyl alcohol, and that the step the solution was cooled to 0? C. in example 22 was amended into the solution was cooled to 45? C., and the step the solution was kept at 0? C., and reacted for 0.5 hour was amended into the solution was kept at 45? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 16.84 ?m. Elemental Analysis (ICP): Ti: 8.19% (by weight), Mg: 12.57% (by weight).

(116) Evaluation of Catalyst:

(117) Slurry polymerization conditions of the catalyst were the same as those in example 22. Results were shown in Table 6.

(118) TABLE-US-00006 TABLE 6 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 22 12.7 63.6 0.36 Example 23 11.2 19.2 0.34 Example 24 15.8 18.7 0.32 Example 25 27.1 21.5 0.34

(119) In the following Examples 26 to 29, a solution of magnesium halide was first prepared. The solution of magnesium halide was then mixed with a halogen and silicon-containing compound to precipitate a solid, thus obtaining a catalyst component.

Example 26

(120) Preparation of a Catalyst Component:

(121) 2.4 g of anhydrous magnesium chloride was measured, followed by addition of 8.8 mL of tetrabutyl titanate, 2.0 mL of epoxy chloropropane, 2.2 mL of anhydrous ethanol, and 50 mL of methylbenzene. The resulting mixture was kept at 60? C. and stirred until a transparent solution was obtained. 100 mL of methylbenzene was again added. The solution was cooled to 0? C., followed by slow drop wise addition of 30 mL of silicon tetrachloride from a burette. After that, the solution was kept at 0? C. and reacted for 0.5 hour, then heated to 50? C. and reacted for 3 hours, and finally heated to 90? C. and reacted for 2 hours, to obtain a suspension liquid of catalyst. The suspension liquid of catalyst was left standing undisturbed for settling, washed for four times with 50 mL of methylbenzene each time, and washed twice with 50 mL of hexane each time. After washing, the liquid was dried with nitrogen sweeping under 65? C. bath condition, to obtain a solid white free-flowing power. The solid white free-flowing power was the catalyst component according to the present invention, and the average particle size thereof was 23.66 ?m. Elemental Analysis: Ti: 0.70% (by weight), Mg: 19.71% (by weight).

(122) Evaluation of Catalyst:

(123) 1 L of hexane, 1 mmol of triethyl aluminum, and a certain amount of catalyst were placed into a 2 L stainless agitated reactor, and then heated to 85? C., followed by addition of 0.18 MPa of hydrogen. The total pressure of the system was maintained at 1.03 MPa with ethylene to run a polymerization reaction. After a 2 hour polymerization reaction, addition of ethylene was stopped, followed by cooling, pressure releasing, weighing of polyethylene powder, calculating of catalyst activity, measuring of bulk density (BD) of the polyethylene powder and melt index (MI2.16) of the polyethylene powder under a load of 2.16 Kg. Results were shown in Table 7.

Example 27

(124) Preparation of a Catalyst Component:

(125) Conditions used in the present example were the same as those used in example 26, except that the step the solution was cooled to 0? C. in example 26 was amended into the solution was cooled to 25? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 25? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 13.78 ?m. Elemental Analysis (ICP): Ti: 0.86% (by weight), Mg: 20.50% (by weight).

(126) Evaluation of Catalyst:

(127) Slurry polymerization conditions of the catalyst were the same as those in example 26. Results were shown in Table 7.

Example 28

(128) Preparation of a Catalyst Component:

(129) Conditions used in the present example were the same as those used in example 26, except that 2.0 mL of epoxy chloropropane in example 26 was changed into 2.1 mL of tetrahydrofuran, and that the step the solution was cooled to 0? C. in example 26 was amended into the solution was cooled to 25? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 25? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 21.61 ?m. Elemental Analysis (ICP): Ti: 0.60% (by weight), Mg: 22.91% (by weight).

(130) Evaluation of Catalyst:

(131) Slurry polymerization conditions of the catalyst were the same as those in example 26. Results were shown in Table 7.

Example 29

(132) Preparation of a Catalyst Component:

(133) Conditions used in the present example were the same as those used in example 26, except that 8.8 mL of tetrabutyl titanate in example 26 was changed into 5.5 mL, of tetraethyl titanate, and that the step the solution was cooled to 0? C. in example 26 was amended into the solution was cooled to 25? C., and the step the solution was kept at 0? C. and reacted for 0.5 hour was amended into the solution was kept at 25? C. and reacted for 0.5 hour. The average particle size of the obtained catalyst was 16.29 ?m. Elemental Analysis (ICP): Ti: 0.36% (by weight), Mg: 19.03% (by weight).

(134) Evaluation of Catalyst:

(135) Slurry polymerization conditions of the catalyst were the same as those in example 26. Results were shown in Table 7.

(136) TABLE-US-00007 TABLE 7 Activity MI.sub.2.16 BD (kgPE/g cat) (g/10 min) (g/ml) Example 26 22.6 0.49 0.38 Example 27 37.4 0.24 0.41 Example 28 17.7 0.33 0.39 Example 29 12.6 0.32 0.39

(137) The above embodiments are merely preferred embodiments of the present invention, and are not provided for restricting the present invention. Any amendments, equivalent substitutions, or improvements can be made to the present invention within the spirit and based on the principles of the present invention.