Spherical supported transition metal catalyst

Abstract

The present invention provides a spherical supported transition metal catalyst. The catalyst carrier is a spherical titanium/zirconium hydrophosphate compound, the primary catalyst is a transition metal compound, the co-catalyst is methylaluminoxane; the spherical titanium/zirconium hydrophosphate compound comprises one or several combinations of titanium hydrophosphate, modified titanium hydrophosphate and zirconium hydrophosphate. The present invention also provides a preparation method of said spherical supported transition metal catalyst and a use thereof in olefin polymerization, as well as the spherical titanium/zirconium hydrophosphate compound and its preparation method. The spherical, supported transition metal catalyst in the present invention has a high catalytic activity, and the polymer particles obtained have good morphology.

Claims

1. A spherical supported transition metal catalyst, wherein a carrier of the catalyst is a spherical titanium hydrophosphate compound or a spherical zirconium hydrophosphate compound, a primary catalyst of the catalyst is a transition metal compound, and a co-catalyst of the catalyst is methylaluminoxane; wherein the spherical titanium hydrophosphate compound or spherical zirconium hydrophosphate compound comprises one or more of titanium hydrophosphate, modified titanium hydrophosphate and zirconium hydrophosphate; and wherein the content of the central metal of the transition metal compound in the catalyst is 0.1 wt % to 0.4 wt %, and the aluminum content in the catalyst is 5 wt % to 20 wt %; wherein the transition metal compound comprises one or more of a metallocene compound and a non-metallocene transition metal compound; wherein the metallocene compound is a metallocene compound having Group IVB transition metal as a central atom and is a silyl bridged metallocene compound; and wherein the non-metallocene transition metal compound is ##STR00018##

2. The spherical supported transition metal catalyst according to claim 1, wherein the modified titanium hydrophosphate comprises an organo-modified titanium hydrophosphate or an acid-modified titanium phosphate.

3. The spherical supported transition metal catalyst according to claim 2, wherein the organo-modified titanium hydrophosphate comprises titanium phenylphosphonate and titanium phenylphosphonate hydrophosphate, and the titanium phenylphosphonate hydrophosphate has a chemical formula of Ti(C.sub.6H.sub.5PO.sub.3).sub.x(HPO.sub.4).sub.2-x, 0<x<2.

4. The spherical supported transition metal catalyst according to claim 3, wherein the chemical formula of the titanium phenylphosphonate hydrophosphate is Ti(C.sub.6H.sub.5PO.sub.3).sub.x(HPO.sub.4).sub.2-x, 0.5x1.5.

5. The spherical supported transition metal catalyst according to claim 2, wherein the acid-modified titanium phosphate comprises sulfuric acid acidified titanium hydrophosphate.

6. The spherical supported transition metal catalyst according to claim 1, wherein the bridged metallocene compound comprises: dimethyl(bis(cyclopentadienyl)silyl)zirconium dichloride, dimethyl(bis(9-fluorenyl)silyl)zirconium dichloride, rac-dimethyl(bis(2-methyl-4,5-benzoindenyl)silyl)zirconium dichloride or rac-dimethyl(bis(2-methyl-4-phenylindenyl)silyl)zirconium dichloride.

7. A method for preparing the spherical supported transition metal catalyst according to claim 1, comprising: dispersing the spherical titanium hydrophosphate compound carrier or the spherical zirconium hydrophosphate compound carrier in toluene and adding thereto methylaluminoxane for treatment to give the activated spherical titanium/zirconium hydrophosphate compound carrier; dissolving the transition metal compound in toluene and adding thereto methylaluminoxane for treatment to give the activated transition metal compound solution; and mixing the activated spherical titanium hydrophosphate compound carrier or the spherical zirconium hydrophosphate compound carrier with the activated transition metal compound solution and stirring to give a mixed mixture, washing and filtering the mixture to obtain a solid precipitate, and drying the solid precipitate to obtain the spherical supported transition metal catalyst.

8. The method for preparing the spherical supported transition metal catalyst according to claim 7, wherein the mass ratio of the transition metal compound to the spherical titanium hydrophosphate compound carrier or the spherical zirconium hydrophosphate compound carrier is (0.01-0.03):1.

9. The method for preparing the spherical supported transition metal catalyst according to claim 7, wherein in preparing the activated spherical titanium hydrophosphate compound carrier or the spherical zirconium hydrophosphate compound carrier, the molar amount of methylaluminoxane is based on the aluminum atom, and the amount ratio of methylaluminoxane to the spherical titanium/zirconium hydrophosphate compound carrier is 3 to 9 mmol/g.

10. The method for preparing the spherical supported transition metal catalyst according to claim 7, wherein in preparing the activated spherical titanium hydrophosphate compound carrier or the spherical zirconium hydrophosphate compound carrier, the molar amount of methylaluminoxane is based on the aluminum atom, and the amount ratio of methylaluminoxane to the spherical titanium hydrophosphate compound carrier or the spherical zirconium hydrophosphate compound carrier is 3 to 9 mmol/g.

11. The method for preparing the spherical supported transition metal catalyst according to claim 7, wherein the methylaluminoxane is added for treatment under the condition of stirring at 1) 20 C. to 50 C. for 20 minutes to 2 hours or 2) 20 C. to 50 C. for 30 minutes to 3 hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a scanning electron micrograph of the spherical titanium hydrophosphate carrier produced in Example 1;

(2) FIG. 2 is a scanning electron micrograph of the spherical supported metallocene catalyst produced in Example 13;

(3) FIG. 3 is a scanning electron micrograph of polyethylene obtained in Example 13;

(4) FIG. 4 is a scanning electron micrograph of polypropylene obtained in Example 28;

(5) FIG. 5 is a transmission electron micrograph of polypropylene obtained in Example 28;

(6) FIG. 6 is a scanning electron micrograph of the spherical supported non-metallocene transition metal catalyst produced in Example 35;

(7) FIG. 7 is a scanning electron micrograph of polyethylene obtained in Example 35; and

(8) FIG. 8 is a transmission electron micrograph of polyethylene obtained in Example 35.

DETAILED DESCRIPTION OF THE INVENTION

(9) In order to understand the technical features, objectives, and advantageous effects of the present invention more clearly, the technical solutions of the present invention will now be described in detail, but it should not be construed as limiting the implementable scope of the present invention.

Example 1

(10) This example provides a spherical titanium hydrophosphate carrier, which is specifically produced by:

(11) accurately weighing 20 g of titanium hydrophosphate (Ti(HPO.sub.4).sub.2), adding thereto 100 g of deionized water, and treating this mixture system with a shear emulsifier at a rotor speed of 10,000 rpm for 30 min, to give a white milky titanium hydrophosphate suspension;

(12) molding the titanium hydrophosphate suspension by a spray dryer having an inlet temperature of 190 C. and an outlet temperature of 110 C.;

(13) heating the obtained solid powder to 160 C. and vacuum drying for 6 h, and then naturally cooling to room temperature under nitrogen protection, to give a spherical titanium hydrophosphate carrier product, designated as sTiP-1 (FIG. 1 is a scanning electron micrograph of sTiP-1).

Example 2

(14) This example provides a spherical titanium hydrophosphate carrier, which is specifically produced by:

(15) accurately weighing 10 g of titanium hydrophosphate (Ti(HPO.sub.4).sub.2), adding thereto 100 g of deionized water, and treating this mixture system with a shear emulsifier at a rotor speed of 10,000 rpm for 30 min, to give a white milky titanium hydrophosphate suspension;

(16) molding the titanium hydrophosphate suspension a spray dryer having an inlet temperature of 200 C. and an outlet temperature of 100 C.;

(17) heating the obtained solid powder to 140 C. and vacuum drying for 6 h, and then naturally cooling to room temperature under nitrogen protection, to give a spherical titanium hydrophosphate carrier product, designated as sTiP-2.

Example 3

(18) This example provides a spherical titanium phenylphosphonate carrier, which is specifically produced by:

(19) accurately weighing 5 g of titanium phenylphosphonate (Ti(C.sub.6H.sub.5PO.sub.3).sub.2), adding thereto 100 g of deionized water, and treating this mixture system with a shear emulsifier at a rotor speed of 8,000 rpm for 30 min, to give a white milky titanium phenylphosphonate suspension;

(20) molding the titanium phenylphosphonate suspension by a spray dryer having an inlet temperature of 180 C. and an outlet temperature of 120 C.;

(21) heating the obtained solid powder to 100 C. and vacuum drying for 4 h, and then naturally cooling to room temperature under nitrogen protection, to give a spherical titanium phenylphosphonate carrier product, designated as sTiBP.

Example 4

(22) This example provides a spherical titanium phenylphosphonate hydrophosphate carrier, which is specifically produced by:

(23) accurately weighing 10 g of titanium phenylphosphonate (Ti(C.sub.6H.sub.5PO.sub.3)(HPO.sub.4)), adding thereto 100 g of deionized water, and treating this mixture system with a shear emulsifier at a rotor speed of 8,000 rpm for 60 min, to give a white milky titanium phenylphosphonate suspension;

(24) molding the titanium phenylphosphonate suspension by a spray dryer having an inlet temperature of 180 C. and an outlet temperature of 120 C.;

(25) heating the obtained solid powder to 150 C. and vacuum drying for 4 h, and then naturally cooling to room temperature under nitrogen protection, to give a spherical titanium phenylphosphonate hydrophosphate carrier product, designated as sTiBPHP.

Example 5

(26) This example provides a spherical sulfuric acid acidified titanium hydrophosphate carrier, which is specifically produced by:

(27) accurately weighing 15 g of titanium hydrophosphate (Ti(HPO.sub.4).sub.2), adding thereto 150 ml 30% sulfuric acid aqueous solution was added, stirring to disperse uniformly, and heating to 95 C., continuing to react for 24 h; after completion of the reaction, lowering to room temperature, and washing the filtered product with deionized water; adding 100 g of deionized water to the product (sulfuric acid acidified titanium hydrophosphate); treating this mixture system with a shear emulsifier at a rotor speed of 10,000 rpm for 30 min, to give a white milky sulfuric acid acidified titanium hydrophosphate suspension;

(28) molding the sulfuric acid acidified titanium hydrophosphate suspension by a spray dryer having an inlet temperature of 200 C. and an outlet temperature of 120 C.;

(29) heating the obtained solid powder to 200 C. and vacuum drying for 4 h, and then naturally cooling to room temperature under nitrogen protection, to give a spherical sulfuric acid acidified titanium hydrophosphate carrier product, designated as sTiP-S.

Example 6

(30) This example provides a spherical zirconium hydrophosphate carrier, which is specifically produced by:

(31) accurately weighing 20 g of zirconium hydrophosphate (Zr(HPO.sub.4).sub.2), adding thereto 90 g of deionized water, and treating this mixture system with a shear emulsifier at a rotor speed of 8,000 rpm for 30 min, to give a white milky zirconium hydrophosphate suspension;

(32) molding the zirconium hydrophosphate suspension by a spray dryer having an inlet temperature of 180 C. and an outlet temperature of 120 C.;

(33) heating the obtained solid powder to 150 C. and vacuum drying for 6 h, and then naturally cooling to room temperature under nitrogen protection to give a spherical zirconium hydrophosphate carrier product, designated as sZrP.

Example 7

(34) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting zirconocene dichloride (Cp.sub.2ZrCl.sub.2), which is specifically prepared by:

(35) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 10 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 20 C. for 20 min, to give an activated carrier;

(36) accurately weighing 100 mg of Cp.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 15 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 20 C. for 20 min, to give an activated Cp.sub.2ZrCl.sub.2 solution;

(37) adding the activated Cp.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 20 C. for 30 min; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-Cp.sub.2ZrCl.sub.2).

(38) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Cp.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 330 gPE/gcat.Math.h.

Example 8

(39) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 2 supporting zirconocene dichloride (Cp.sub.2ZrCl.sub.2), which is specifically prepared by:

(40) accurately weighing 5 g of sTiP-2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 30 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 50 C. for 2 h to give an activated carrier;

(41) accurately weighing 150 mg of Cp.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 15 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 3 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 50 C. for 2 h to give an activated Cp.sub.2ZrCl.sub.2 solution;

(42) adding the activated Cp.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 50 C. for 3 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-2-Cp.sub.2ZrCl.sub.2).

(43) Into a 2 L stainless steel autoclave for polymerizaiton sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-2-Cp.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 400 gPE/gcat.Math.h.

Example 9

(44) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 3 supporting zirconocene dichloride (Cp.sub.2ZrCl.sub.2), which is specifically prepared by:

(45) accurately weighing 5 g of sTiBP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 25 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated carrier;

(46) accurately weighing 100 mg of Cp.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 15 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 20 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated Cp.sub.2ZrCl.sub.2 solution;

(47) adding the activated Cp.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiBP-Cp.sub.2ZrCl.sub.2).

(48) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiBP-Cp.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 120 gPE/gcat.Math.h.

Example 10

(49) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 4 supporting zirconocene dichloride (Cp.sub.2ZrCl.sub.2), which is specifically prepared by:

(50) accurately weighing 5 g of sTiBPHP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated carrier;

(51) accurately weighing 100 mg of Cp.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 15 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 2 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated Cp.sub.2ZrCl.sub.2 solution;

(52) adding the activated Cp.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiBPHP-Cp.sub.2ZrCl.sub.2).

(53) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiBPHP-Cp.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 220 gPE/gcat.Math.h.

Example 11

(54) This example provides a spherical supported metallocene catalyst, which is prepared from the carrier in Example 5 loaded with zirconocene dichloride (Cp.sub.2ZrCl.sub.2), which is specifically prepared by:

(55) accurately weighing 5 g of sTiP-S under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated carrier;

(56) accurately weighing 50 mg of Cp.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 15 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated Cp.sub.2ZrCl.sub.2 solution;

(57) adding the activated Cp.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-S-Cp.sub.2ZrCl.sub.2).

(58) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-S-Cp.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 500 gPE/gcat.Math.h.

Example 12

(59) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting bisindenylzirconium dichloride (Ind.sub.2ZrCl.sub.2), which is specifically prepared by:

(60) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated carrier;

(61) accurately weighing 60 mg of Ind.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 15 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 30 C. for 1 h to give an activated Ind.sub.2ZrCl.sub.2 solution;

(62) adding the activated Ind.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-Ind.sub.2ZrCl.sub.2).

(63) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Ind.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 530 gPE/gcat.Math.h.

Example 13

(64) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting bis(n-butylcyclopentadienyl)zirconium dichloride ((nBuCp).sub.2ZrCl.sub.2), which is specifically prepared by:

(65) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(66) accurately weighing 70 mg of (nBuCp).sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated (nBuCp).sub.2ZrCl.sub.2 solution;

(67) adding the activated (nBuCp).sub.2ZrCl.sub.2 solution the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-(nBuCp).sub.2ZrCl.sub.2, of which the scanning electron micrograph is shown in FIG. 2).

(68) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-(nBuCp).sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h (the scanning electron micrograph of the obtained polyethylene product is shown in FIG. 3); the activity of the catalyst was measured to be 2300 gPE/gcat.Math.h.

Example 14

(69) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting fluorenylcyclopentadienylzirconium dichloride (FluCpZrCl.sub.2), which is specifically prepared by:

(70) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(71) accurately weighing 100 mg of FluCpZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated FluCpZrCl.sub.2 solution;

(72) adding the activated FluCpZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-FluCpZrCl.sub.2).

(73) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-FluCpZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 600 gPE/gcat.Math.h.

Example 15

(74) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting bis(tert-butylcyclopentadienyl)hafnium dichloride ((tBuCp).sub.2HfCl.sub.2), which is specifically prepared by:

(75) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(76) accurately weighing 100 mg of (tBuCp).sub.2HfCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated (tBuCp).sub.2HfCl.sub.2 solution;

(77) adding the activated (tBuCp).sub.2HfCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-(tBuCp).sub.2HfCl.sub.2).

(78) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-(tBuCp).sub.2HfCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 2100 gPE/gcat.Math.h.

Example 16

(79) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting bis(tert-butylcyclopentadienyl)dimethylhafnium ((BuCp).sub.2Hf(CH.sub.3).sub.2), which is specifically prepared by:

(80) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(81) accurately weighing 100 mg of (BuCp).sub.2Hf(CH.sub.3).sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated (BuCp).sub.2Hf(CH.sub.3).sub.2 solution;

(82) adding the activated (BuCp).sub.2Hf(CH.sub.3).sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-(BuCp).sub.2Hf(CH.sub.3).sub.2).

(83) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-(BuCp).sub.2Hf(CH.sub.3).sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 1810 gPE/gcat.Math.h.

Example 17

(84) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 6 supporting cyclopentadienyltitanium trichloride (CpTiCl.sub.3), which is specifically prepared by:

(85) accurately weighing 5 g of sZrP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 20 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(86) accurately weighing 50 mg of CpTiCl.sub.3 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated CpTiCl.sub.3 solution;

(87) adding the activated CpTiCl.sub.3 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sZrP-CpTiCl.sub.3).

(88) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sZrP-CpTiCl.sub.3, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 80 gPE/gcat.Math.h.

Example 18

(89) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 6 supporting indenyltitanium trichloride (IndTiCl.sub.3), which is specifically prepared by:

(90) accurately weighing 5 g of sZrP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 20 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(91) accurately weighing 50 mg of IndTiCl.sub.3 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated IndTiCl.sub.3 solution;

(92) adding the activated IndTiCl.sub.3 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sZrP-IndTiCl.sub.3).

(93) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sZrP-IndTiCl.sub.3, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 100 gPE/gcat.Math.h.

Example 19

(94) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 6 supporting pentamethycyclopentadienyltitanium trichloride (Cp*TiCl.sub.3), which is specifically prepared by:

(95) accurately weighing 5 g of sZrP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 20 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(96) accurately weighing 50 mg of Cp*TiCl.sub.3 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Cp*TiCl.sub.3 solution;

(97) adding the activated Cp*TiCl.sub.3 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sZrP-Cp*TiCl.sub.3).

(98) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sZrP-Cp*TiCl.sub.3, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 110 gPE/gcat.Math.h.

Example 20

(99) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 6 supporting pentamethycyclopentadienylzirconium trichloride (Cp*ZrCl.sub.3), which is specifically prepared by:

(100) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 20 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(101) accurately weighing 50 mg of Cp*ZrCl.sub.3 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Cp*ZrCl.sub.3 solution;

(102) adding the activated Cp*ZrCl.sub.3 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-Cp*ZrCl.sub.3).

(103) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Cp*ZrCl.sub.3, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 100 gPE/gcat.Math.h.

Example 21

(104) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 6 supporting dimethyl(bis(cyclopentadienyl)silyl)zirconium dichloride (Me.sub.2SiCp.sub.2ZrCl.sub.2), which is specifically prepared by:

(105) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(106) accurately weighing 50 mg of Me.sub.2SiCp.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Me.sub.2SiCp.sub.2ZrCl.sub.2 solution;

(107) adding the activated Me.sub.2SiCp.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-Me.sub.2SiCp.sub.2ZrCl.sub.2).

(108) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Me.sub.2SiCp.sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 450 gPE/gcat.Math.h.

Example 22

(109) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting dimethyl(bis(9-fluorenyl)silyl)zirconium dichloride (Me.sub.2Si(9-Flu).sub.2ZrCl.sub.2), which is specifically prepared by:

(110) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(111) accurately weighing 100 mg of Me.sub.2Si(9-Flu).sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 5 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Me.sub.2Si(9-Flu).sub.2ZrCl.sub.2 solution;

(112) adding the activated Me.sub.2Si(9-Flu).sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-Me.sub.2Si(9-Flu).sub.2ZrCl.sub.2).

(113) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Me.sub.2Si(9-Flu).sub.2ZrCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 340 gPE/gcat.Math.h.

Example 23

(114) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting isopropylidenebis(9-fluorenyl)zirconium dichloride (iPr(9-Flu).sub.2ZrCl.sub.2), which is specifically prepared by:

(115) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(116) accurately weighing 100 mg of iPr(9-Flu).sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 5 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated iPr(9-Flu).sub.2ZrCl.sub.2 solution;

(117) adding the activated iPr(9-Flu).sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-iPr(9-Flu).sub.2ZrCl.sub.2).

(118) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-iPr(9-Flu).sub.2ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h; the activity of the catalyst was measured to be 210 gPP/gcat.Math.h.

Example 24

(119) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (iPrCp(9-Flu)ZrCl.sub.2), which is specifically prepared by:

(120) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(121) accurately weighing 100 mg of iPrCp(9-Flu)ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 5 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated iPrCp(9-Flu)ZrCl.sub.2 solution;

(122) adding the activated iPrCp(9-Flu)ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-iPrCp(9-Flu)ZrCl.sub.2).

(123) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-iPrCp(9-Flu)ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h; the activity of the catalyst was measured to be 200 gPP/gcat.Math.h.

Example 25

(124) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (Ph.sub.2CCp(9-Flu)ZrCl.sub.2), which is specifically prepared by:

(125) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(126) accurately weighing 100 mg of Ph.sub.2CCp(9-Flu)ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 5 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Ph.sub.2CCp(9-Flu)ZrCl.sub.2 solution;

(127) adding the activated Ph.sub.2CCp(9-Flu)ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-Ph.sub.2CCp(9-Flu)ZrCl.sub.2).

(128) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Ph.sub.2CCp(9-Flu)ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h; the activity of the catalyst was measured to be 250 gPP/gcat.Math.h.

Example 26

(129) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting rac-ethylenebisindenylzirconium dichloride (rac-EtInd.sub.2ZrCl.sub.2), which is specifically prepared by:

(130) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(131) accurately weighing 60 mg of rac-EtInd.sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 10 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated rac-EtInd.sub.2ZrCl.sub.2 solution;

(132) adding the activated rac-EtInd.sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-rac-EtInd.sub.2ZrCl.sub.2).

(133) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-rac-EtInd.sub.2ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h; the activity of the catalyst was measured to be 1500 gPP/gcat.Math.h.

Example 27

(134) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting rac-ethylenebis(tetrahydroindenyl)zirconium dichloride (rac-Et(IndH.sub.4).sub.2ZrCl.sub.2), which is specifically prepared by:

(135) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(136) accurately weighing 100 mg of rac-Et(IndH.sub.4).sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 10 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated rac-Et(IndH.sub.4).sub.2ZrCl.sub.2 solution;

(137) adding the activated rac-Et(IndH.sub.4).sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-rac-Et(IndH.sub.4).sub.2ZrCl.sub.2).

(138) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-rac-Et(IndH.sub.4).sub.2ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h; the activity of the catalyst was measured to be 1830 gPP/gcat.Math.h.

Example 28

(139) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting rac-dimethyl(bis(2-methyl-4,5-benzoindenyl)silyl)zirconium dichloride (rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2), which is specifically prepared by:

(140) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(141) accurately weighing 100 mg of rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 20 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 10 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2 solution;

(142) adding the activated rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2).

(143) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h (the scanning electron micrograph of the obtained polypropylene product is shown in FIG. 4); the activity of the catalyst was measured to be 2130 gPP/gcat.Math.h.

(144) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-rac-Me.sub.2Si(2-Me-4,5-BenzInd).sub.2ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 30 min, to give 50 g of polypropylene. FIG. 5 is a transmission electron micrograph of polypropylene (polymerization reaction was only allowed to proceed at 60 C. for 30 min, so that the content of the carrier in the polymer is relatively high, and it is easy to observe the distribution of the carrier in the polymer). In this figure, the scale is 6 nm, and the black part is the carrier. From this figure, it is known that the carrier is uniformly dispersed in the polymer in a nano-scale.

Example 29

(145) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting rac-dimethyl(bis(2-methyl-4-phenylindenyl)silyl)zirconium dichloride (rac-Me.sub.2Si(2-Me-4-PhInd).sub.2ZrCl.sub.2), which is specifically prepared by:

(146) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(147) accurately weighing 100 mg of rac-Me.sub.2Si(2-Me-4-PhInd).sub.2ZrCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 10 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated rac-Me.sub.2Si(2-Me-4-PhInd).sub.2ZrCl.sub.2 solution;

(148) adding the activated rac-Me.sub.2Si(2-Me-4-PhInd).sub.2ZrCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sTiP-1-rac-Me.sub.2Si(2-Me-4-PhInd).sub.2ZrCl.sub.2).

(149) Into a 5 L stainless steel autoclave for polymerization sufficiently substituted with nitrogen, 1 kg of liquid propylene was added, 1 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-rac-Me.sub.2Si(2-Me-4-PhInd).sub.2ZrCl.sub.2, the temperature was raised to 60 C. and the reaction was allowed to proceed for 2 h; the activity of the catalyst was measured to be 2400 gPP/gcat.Math.h.

Example 30

(150) This example provides a spherical supported metallocene catalyst produced from the carrier of Example 1 supporting [Me.sub.2Si(Me.sub.4Cp)(NtBu)]TiCl.sub.2

(151) ##STR00006##
which is specifically prepared by:

(152) accurately weighing 5 g of sZrP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(153) accurately weighing 100 mg of [Me.sub.2Si(Me.sub.4Cp)(NtBu)]TiCl.sub.2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 2 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated [Me.sub.2Si(Me.sub.4Cp)(NtBu)]TiCl.sub.2 solution;

(154) adding the activated [Me.sub.2Si(Me.sub.4Cp)(NtBu)]TiCl.sub.2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported metallocene catalyst (designated as sZrP-[Me.sub.2Si(Me.sub.4Cp)(NtBu)]TiCl.sub.2).

(155) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sZrP-[Me.sub.2Si(Me.sub.4Cp)(NtBu)]TiCl.sub.2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 2300 gPE/gcat.Math.h.

Example 31

(156) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(157) ##STR00007##
which is specifically prepared by:

(158) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(159) accurately weighing 120 mg of Nicat1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 2 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Nicat1 solution;

(160) adding the activated Nicat1 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Nicat1).

(161) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Nicat1, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 620 gPE/gcat.Math.h.

Example 32

(162) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(163) ##STR00008##
which is specifically prepared by:

(164) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated carrier;

(165) accurately weighing 100 mg of Nicat2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Nicat2 solution;

(166) adding the activated Nicat2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Nicat2).

(167) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Nicat2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 650 gPE/gcat.Math.h.

Example 33

(168) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(169) ##STR00009##
which is specifically prepared by:

(170) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(171) accurately weighing 100 mg of Pdcat under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Pdcat solution;

(172) adding the activated Pdcat solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Pdcat).

(173) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Pdcat, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 180 gPE/gcat.Math.h.

Example 34

(174) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting 2,6-bis[1-(2,6-dimethyl-4-(3-hydroxypropyl)phenylimino)ethylene]pyridineiron(II) chloride (Fecat1), which is specifically prepared by:

(175) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(176) accurately weighing 100 mg of Fecat1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 2 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Fecat1 solution;

(177) adding the activated Fecat1 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Fecat1).

(178) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Fecat1, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 2000 gPE/gcat.Math.h.

Example 35

(179) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting [2-(1-(2,4,6-trimethyl-(3-amino)phenyl)imino)ethyl][6-(1-(2,6-diisopropylphenylimino)ethyl]pyridine iron (II) chloride

(180) ##STR00010##
which is specifically prepared by:

(181) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 15 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(182) accurately weighing 100 mg of Fecat2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Fecat2 solution;

(183) adding the activated Fecat2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Fecat2); FIG. 6 is a scanning electron micrograph of sTiP-1-Fecat2.

(184) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Fecat2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 2230 gPE/gcat.Math.h; FIG. 7 is a scanning electron micrograph of the obtained polyethylene.

(185) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Fecat2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 10 min, to give 40 g of polyethylene. FIG. 8 is a transmission electron micrograph of the obtained polyethylene (polymerization reaction was only allowed to proceed at 60 C. for 10 min, so that the content of the carrier in the polymer is relatively high, and it is easy to observe the distribution of the carrier in the polymer). In this figure, the scale is 6 nm, and the black part is carrier. From this figure, it is known that the carrier is uniformly dispersed in the polymer in a nano-scale.

Example 36

(186) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 6 supporting

(187) ##STR00011##
which is specifically prepared by:

(188) accurately weighing 5 g of sZrP under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(189) accurately weighing 100 mg of Ticat under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Ticat solution;

(190) adding the activated Pdcat solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sZrP-Ticat).

(191) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sZrP-Ticat, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 1750 gPE/gcat.Math.h.

Example 37

(192) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(193) ##STR00012##
which is specifically prepared by:

(194) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(195) accurately weighing 100 mg of Zrcat under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Zrcat solution;

(196) adding the activated Zrcat solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Zrcat).

(197) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Zrcat, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 2400 gPE/gcat.Math.h.

Example 38

(198) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(199) ##STR00013##
which is specifically prepared by:

(200) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(201) accurately weighing 100 mg of Vcat1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Vcat1 solution;

(202) adding the activated Vcat1 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Vcat1).

(203) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Vcat1, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 800 gPE/gcat.Math.h.

Example 39

(204) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(205) ##STR00014##
which is specifically prepared by:

(206) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(207) accurately weighing 150 mg of Vcat2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Vcat2 solution;

(208) adding the activated Vcat2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Vcat2).

(209) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Vcat2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 760 gPE/gcat.Math.h.

Example 40

(210) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(211) ##STR00015##
which is specifically prepared by:

(212) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(213) accurately weighing 150 mg of Crcat under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 1 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated Crcat solution;

(214) adding the activated Crcat solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-Crcat).

(215) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-Crcat, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 310 gPE/gcat.Math.h.

Example 41

(216) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(217) ##STR00016##
which is specifically prepared by:

(218) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(219) accurately weighing 100 mg of NiCocat1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 2 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated NiCocat1 solution;

(220) adding the activated NiCocat1 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-NiCocat1).

(221) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-NiCocat1, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 750 gPE/gcat.Math.h.

Example 42

(222) This example provides a spherical supported non-metallocene transition metal catalyst produced from the carrier of Example 1 supporting

(223) ##STR00017##
which is specifically prepared by:

(224) accurately weighing 5 g of sTiP-1 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 25 ml of dewatered refined toluene; after stirring to disperse it uniformly, adding thereto 16 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 2 h to give an activated carrier;

(225) accurately weighing 100 mg of NiCocat2 under nitrogen protection into a glass reactor sufficiently substituted with nitrogen, and adding thereto 50 ml of dewatered refined toluene; after stirring to dissolve it completely, adding thereto 2 ml of methylaluminoxane (1.5 M toluene solution) and stirring at 40 C. for 1 h to give an activated NiCocat2 solution;

(226) adding the activated NiCocat2 solution to the activated carrier under nitrogen protection and stirring at 40 C. for 2 h; after completion of the reaction, leaving to stand, and filtering off the liquid after layering; washing the mixture twice with 20 ml of dewatered refined toluene, and twice with 30 ml of dewatered refined hexane; vacuum drying the solid to give a spherical supported non-metallocene transition metal catalyst (designated as sTiP-1-NiCocat2).

(227) Into a 2 L stainless steel autoclave for polymerization sufficiently substituted with ethylene, 1 L of dewatered refined hexane was added, 2 ml of triethylaluminum (2.4 M in hexane) was added, followed by the addition of 100 mg of the catalyst sTiP-1-NiCocat2, ethylene was introduced, the pressure was raised and maintained at 1.0 MPa, and the reaction was allowed to proceed at 60 C. for 1 h; the activity of the catalyst was measured to be 970 gPE/gcat.Math.h.