Supported metal oxide double active center polyethylene catalyst, process for preparing the same and use thereof

Abstract

The present invention relates to a supported hybrid vanadium-chromium-based catalyst, characterized in the catalyst is supported on a porous inorganic carrier and a V active site and a inorganic Cr active site are present on the porous inorganic carrier at the same time. The present invention further relates to a process for producing a supported hybrid vanadium-chromium-based catalyst. The invention also provides the preparation method of the catalyst, titanium or fluorine compounds, vanadium salt and chromium salt according to the proportion, different methods of sequence and load on the inorganic carrier, after high temperature roasting, still can further add organic metal catalyst promoter prereduction activation treatment on it. The catalyst of the present invention can be used for producing ethylene homopolymers and ethylene/α-olefin copolymers. The hybrid vanadium-chromium-based catalyst can have high activity and produce polyethylene polymers having the properties of broad molecular weight distribution (Part of the products are bimodal distribution) and excellent α-olefin copolymerization characteristic.

Claims

1. A supported hybrid vanadium-chromium-based catalyst, characterized in that the catalyst is supported on a porous inorganic carrier and wherein an inorganic chromium active site and vanadium active site are present on the porous inorganic carrier; the chromium precursor and vanadium precursor are presented on the porous inorganic carrier as supported Cr/V metal oxide double active centers by one of the following processes of chemisorption or physical adsorption followed by drying and calcination at high temperature: i) impregnating the porous inorganic carrier into a solution of the vanadium precursor, drying and calcining at 300˜900° C., and ii) impregnating the product obtained in step i) into a solution of the chromium precursor, drying and calcining at 300˜900° C.; or i) impregnating the porous inorganic carrier into a solution of the chromium precursor, drying and calcining at 300˜900° C., and ii) impregnating the product obtained in step i) into a solution of the vanadium precursor, drying and calcining at 300˜900° C.; or impregnating the porous inorganic carrier into a solution of the chromium and vanadium precursor, drying and calcining at 300˜900° C.

2. The catalyst according to claim 1, wherein said porous inorganic carrier is modified with titanium and fluorine.

3. The catalyst according to claim 1, wherein the porous inorganic carrier is selected from the group consisting of silica, alumina, titania, zirconia, magnesia, calcium oxide and inorganic clays, and combinations thereof.

4. The catalyst according to claim 1, wherein the porous inorganic carrier has a surface area from 50 to 500 m.sup.2/g.

5. The catalyst according to claim 1, wherein the porous inorganic carrier has a pore volume from 0.1 to 5.0 cm.sup.3/g, and an average pore diameter of 1 to 50 nm.

6. The catalyst according to claim 1, wherein the chromium loading on the porous inorganic carrier is, based on the weight of chromium, from 0.01 to 10 wt. % of the total weight of the catalyst.

7. The catalyst according to claim 1, wherein the ratio of the vanadium loading to the chromium loading on the carrier is 0.1 to 5 based on the weight of chromium and vanadium.

8. The catalyst according to claim 1, wherein the vanadium loading on the porous inorganic carrier is, based on the weight of vanadium, from 0.01 to 10 wt. % of the total weight of the catalyst.

9. The catalyst according to claim 1, wherein the chromium precursor of the chromium active site is selected from chromium trioxide, nitric acid chromium, acetic acid chromium, chromium chloride, chromium acid ammonium sulfate, ammonium dichromate and alkali type chromium acetate and combinations thereof.

10. The catalyst according to claim 1, wherein the vanadium precursor of the V active site is selected from vanadic nitrate, vanadic phosphate, vanadic sulfate, vanadic acetate, ammonium hexafluorovanadate, vanadic acetate, vanadic nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium sulfate oxide hydrate, vanadic sulfate, vanadyl trichloride, sodium orthovanadate, sodium metavanadate, vanadyl bis (acetylacetone), vanadic triisopropoxide oxide, vanadic oxytripropoxide, vanadic acetylacetone, vanadic oxytriethoxide, vanadyl chloride, vanadic silicide, and combinations thereof.

11. The catalyst according to claim 2, wherein the titanium loading on the porous inorganic carrier is, based on the weight of chromium, from 0.01 to 30 wt. % of the total weight of the catalyst.

12. The catalyst according to claim 2, wherein the fluorine loading on the porous inorganic carrier is, based on the weight of fluorine, from 0.01 to 10 wt. % of the total weight of the catalyst.

13. The catalyst according to claim 2, wherein the titanium is selected from acetylacetone titanium oxide, titanium trichloride, titanium tetrachloride, tertiary butanol titanium, tetra-n-butyl titanate, titanium oxide sulfate, titanium sulfate, ammonium hexafluorotitanate, titanium isopropoxide, tetraethyl titanate, and soluble titanium salt combinations thereof.

14. The catalyst according to claim 2, wherein the fluorine is selected from hydrogen fluoride and fluorine gas, ammonium fluoride, ammonium fluoride, ammonium fluoride boric acid, or fluoboric acid copper, silver fluoboric acid, or fluoboric acid gold, fluosilicic acid copper, fluosilicic acid copper, silver fluosilicate, ammonium fluosilicate gold, fluoboric acid, or hexafluoride ammonium vanadate, six ammonium fluosilicate, fluoboric acid zinc, magnesium silicate fluoride, zinc fluoride silicate, sodium fluoboric acid, soluble fluoride salt or combinations thereof.

15. The catalyst according to claim 2, wherein the porous inorganic carrier is prepared by one process selected from the following four processes: (1) an immersion method in which a titanium compound is dissolved in solvent and reacted with and inorganic carrier, dried, then under a temperature of 300 to 900° C. undergoes calcination activation, to obtain a titanium dioxide modified inorganic carrier; (2) a coprecipitation method in which a titanium compound and a silicate compound are reacted, dried, then under a temperature of 300 to 900° C. undergoes calcination activation, to obtain a titanium dioxide modified inorganic carrier; (3) a sol-gel application method in which a titanium compound is mixed with water and anhydrous ethanol to undergo a hydrolysis reaction, then is further reacted with an inorganic acid and an inorganic carrier, dried, then under a temperature of 300 to 900° C. undergoes calcination activation, to obtain a titanium dioxide modified inorganic carrier; and (4) a sol-gel application method in which a titanium compound is stirred in organic solvents, then is reacted with an inorganic acid in an acid reflux reaction, then is further reacted with an inorganic carrier, dried, then under a temperature of 300 to 900° C. undergoes calcination activation, to obtain a titanium dioxide modified inorganic carrier.

16. The catalyst according to claim 15, wherein the silicate compound is selected from aluminum silicate, sodium silicate, ethyl silicate, magnesium silicate and calcium silicate, soluble silica salt and combinations thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 represents the process of treating the silica gel support or the catalyst precursor.

(2) FIG. 2 represents the process of treating the silica gel support or the catalyst precursor.

(3) FIG. 3 represents the GPC curves of 3 polymers obtained from ethylene homopolymerization (Example 10, 11 and 20).

(4) FIG. 4 represents the GPC curves of 3 polymers obtained from ethylene/1-hexene copolymerization (Example 12, 13 and 21).

(5) FIG. 5 represents the process of treating the silica gel support or the catalyst precursor.

(6) FIG. 6 represents the GPC curves of 3 polymers obtained from ethylene homopolymerization (Comparison Example 16-1, Example 37 and 38-1).

(7) FIG. 7 represents the GPC curves of 3 polymers obtained from ethylene homopolymerization (Comparison Example 16-1, Example 39).

(8) FIG. 8 represents the process of treating the silica gel support or the catalyst precursor.

DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

(9) The present invention is more detailedly illustrated by reference to the following examples, but is not limited by these examples.

(10) The silica gel used in the examples is Davison 955 or 948.

(11) Cases of various polymer properties according to the following method:

(12) High temperature and gel chromatography (HT-GPC)

(13) Weight average molecular weight and molecular weight distribution with high temperature and gel chromatography determination: this experiment adopts the PL-220 type high temperature gel permeation chromatograph (Polymer Laboratories company) to determine polyethylene molecular weight and molecular weight distribution. Experiment 1,2,4-trichlorobenzene as solvent, the determination of under 160° C. A narrow distribution polystyrene as the prototype of the universal correction method of data processing.

(14) Differential Scanning Calorimetry (DSC)

(15) Test of polymer melting point: this experiment adopts the TA Q200 type under nitrogen protection differential scanning calorimeter test. Sample first with 10° C./min speed from room temperature to heat up to 150° C., and constant temperature for 5 min, then down to room temperature naturally. Then heat up with 10° C./min speed scan (at room temperature to 150° C.), DSC curve.

Example 1

(16) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of vanadyl oxalate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 5 h, the silica gel support supporting the vanadyl oxalate was high-temperature calcined in a fluidized bed. Finally, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 2

(17) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of alkali type chromium acetate and ammonium metavanadate at 40° C., enabled the vanadium and chromium loading (based on the mass of V and Cr) to be 0.48% and 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 3

(18) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of vanadyl sulfate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.16%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 4

(19) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed in 450° C. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 5

(20) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an alcohol solution of Diacetyl acetone vanadium oxide at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 6

(21) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of alkali type chromium acetate, enabled the Cr loading (based on the mass of Cr) to be 0.24%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of sodium metavanadate at 40° C., enabled the V loading (based on the mass of V) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 7

(22) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed in 450° C. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then used organometallic co-catalysts MAO to pre-reduction the catalyst precursor, the concentration of co-catalyst was 1.0 mmol/mL. Finally drying at 100° C. for 4 h, the drying is conducted under an inert gas atmosphere.

Example 8

(23) 160 mg of the catalyst in Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 9

(24) 160 mg of the catalyst in Example 2 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 10

(25) 160 mg of the catalyst in Example 3 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 11

(26) 160 mg of the catalyst in Example 5 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=20. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 12

(27) 160 mg of the catalyst in Example 6 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 13

(28) 160 mg of the catalyst in Example 7 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration, Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 14

(29) 160 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 15

(30) 160 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5, 10, 15 and 20 (Example 15-1, 15-2, 15-3 and 15-4). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 16

(31) 160 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 50° C. and 70° C. for 1 h (Example 16-1, 16-2), a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 17

(32) 160 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 18

(33) 160 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. The amount of 1-hexene was respectively 0.7 mL, 2.1 mL, and 3.5 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 1 vol % (Example 18-1), 3 vol % (Example 18-2) and 5 vol % (Example 18-3). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 19

(34) 160 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL hydrogen and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 20

(35) 100 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 200 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.4 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 21

(36) 100 mg of the catalyst in Example 4 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 200 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. The amount of 1-hexene was respectively 6 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 3 vol %. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 1

(37) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of alkali type chromium acetate, enabled the Cr loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, the silica gel support supporting the alkali type chromium acetate was high-temperature calcined in a fluidized bed and obtained Phillips catalyst.

Comparison Example 2

(38) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium metavanadate, enabled the V loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, the silica gel support supporting the alkali type chromium acetate was high-temperature calcined in a fluidized bed and obtained vanadium catalyst.

Comparison Example 3

(39) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of alkali type chromium acetate, enabled the Cr loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, the silica gel support supporting the alkali type chromium acetate was high-temperature calcined in a fluidized bed and obtained Phillips catalyst. And 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium metavanadate, enabled the V loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, the silica gel support supporting the alkali type chromium acetate was high-temperature calcined in a fluidized bed and obtained vanadium catalyst. Then mix the Phillips catalyst and vanadium catalyst to obtain a mixture catalyst.

Comparison Example 4

(40) 160 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 5

(41) 160 mg of the catalyst in Comparison Example 2 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/V (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 6

(42) 160 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 90° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 7

(43) 160 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. The amount of 1-hexene was respectively 0.7 mL, 2.1 mL, and 3.5 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 1 vol % (Comparison Example 7-1), 3 vol % (Comparison Example 7-2) and 5 vol % (Comparison Example 7-3). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 8

(44) 160 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL hydrogen and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 9

(45) 160 mg of the catalyst in Comparison Example 2 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL hydrogen and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 10

(46) 100 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 200 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.4 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 11

(47) 100 mg of the catalyst in Comparison Example 2 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 200 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.4 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 12

(48) 100 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 200 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. The amount of 1-hexene was respectively 6 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 3 vol %. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 13

(49) 100 mg of the catalyst in Comparison Example 2 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 200 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. The amount of 1-hexene was respectively 6 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 3 vol %. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

(50) TABLE-US-00001 TABLE 1 Polymerization activities of examples Activity (kg.sub.PE/mol Example Cr or V h) Example 8 139.4 Example 9 88.4 Example 10 75.9 Example 11 73.8 Example 12 80.1 Example 13 70.7 Example 14 96.7 Example 15-1 145.6 Example 15-2 111.3 Example 15-3 87.4 Example 15-4 82.2 Example 16-1 535.6 Example 16-2 325.5 Example 17 103.0 Example 18-1 127.9 Example 18-2 124.8 Example 18-3 122.7 Example 19 157.0 Example 20 1690.0 Example 21 907.9 Comparison Example 4 101.9 Comparison Example 5 36.1 Comparison Example 6 80.1 Comparison Example 7-1 111.3 Comparison Example 7-2 104.0 Comparison Example 7-3 72.8 Comparison Example 8 110.2 Comparison Example 9 79.0 Comparison Example 10 670.8 Comparison Example 11 274.1 Comparison Example 12 536.6 Comparison Example 13 225.3
(1) Comparison of Different Amount of Cocatalyst

(51) TABLE-US-00002 TABLE 2 Comparison of different amount of cocatalyst in ethylene homopolymerization activity (kg PE/mol T.sub.m M.sub.w Example co-catalyst Al/Cr Cr h) (° C.) (×10.sup.5) PDI Example 14 — 0 96.7 132.07 3.09 28.6 Example TIBA 5 145.6 132.16 2.76 30.1 15-1 Example TIBA 10 111.3 132.96 3.15 29.8 15-2 Example TIBA 15 87.4 133.51 3.49 29.3 15-3 Example TIBA 20 82.2 133.60 3.52 29.5 15-4 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; polymerization temperature = 90° C.; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.

(52) Represented by Example 14 and 15, examines the Cr—V catalyst in different amount of cocatalyst by ethylene homopolymerization, result in table 2.

(53) From table 2 shows that under the condition of TIBA as cocatalyst, as cocatalyst Al/Cr than from 5 to 20 increasing, Cr—V catalyst toward a reduction in the activity of catalyst in ethylene homopolymerization process, instructions to achieve highly active polymerization, the dosage of the catalyst promoter is an appropriate value or range, catalyst in the Al/Cr is 5, the highest activity.

(54) TABLE-US-00003 TABLE 3 Comparison of Cr—V catalyst and Phillips catalyst activity (kg PE/ mol M.sub.w Example co-catalyst Al/Cr Cr h) T.sub.m (° C.) (×10.sup.5) PDI Comparison TIBA 5 101.9 132.11 2.52 28.2 Example 4 Comparison TEA 5 79.0 131.07 1.73 19.9 Example 9 Example 15-1 TIBA 5 145.6 132.16 2.76 30.1 Example 17 TEA 5 103.0 131.44 1.94 33.8 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; polymerization temperature = 90° C.; n-heptane = 70 mL; Cr = 0.5% (wt); co-catalyst = TIBA.

(55) Table 3 according to different cocatalyst double active center of chrome vanadium catalyst and the effect of ethylene homopolymerization Phillips catalyst activity. By TEA as cocatalyst activity below made cocatalyst TiBA. Further through the analysis of the above product polyethylene, under different cocatalyst is the melting point of polyethylene products have similar, but its very different molecular weight and molecular weight distribution, showed the cocatalyst to the center of the catalyst activity after reduction degree and reduction of distribution has great influence.

(56) (2) Comparison of Temperature

(57) TABLE-US-00004 TABLE 4 Comparison of temperature activity (kg PE/ mol Cr M.sub.w Example temp. Al/Cr h) T.sub.m (° C.) (× 10.sup.5) PDI Example 16-1 50 5 535.6 132.35 3.65 29.4 Example 16-2 70 5 325.5 132.28 3.39 13.8 Example 15-1 90 5 145.6 132.16 2.76 30.1 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.

(58) Table 4 for the different polymerization temperature (Example 15-1 and Example 16) of chrome vanadium double active center of ethylene polymerization catalyst. At 50° C. with the highest catalyst activity, with the increase of temperature of catalyst activity decreases, the lowest activity at 90° C. Under different temperature of the melting point of polyethylene products have similar, its molecular weight with the increase of polymerization temperature, the trend of decrease, chain transfer reaction shows polymerization temperature on polymerization more advantageous.

(59) (3) Comparison of Different Preparation of Catalyst

(60) TABLE-US-00005 TABLE 5 Comparison of different preparation of catalyst activity (kg PE/ T.sub.m M.sub.w Example co-catalyst Al/Cr mol Cr h) (° C.) (×10.sup.5) Example 8 5 139.4 131.85 2.16 25.8 Example 9 5 88.4 131.04 1.97 25.4 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.

(61) Example 8 and 9 are two step impregnation and total immersion respectively in different load method preparation of chrome vanadium catalyst in the same conditions of polymerization activity, visible by dipping the preparation of composite catalyst activity is higher.

(62) (4) Comparison of Different Dosage of 1-Hexene

(63) TABLE-US-00006 TABLE 6 Comparison of different dosage of 1-hexene activity (kg PE/ mol Cr M.sub.w Example 1-hexene Al/Cr h) T.sub.m (° C.) (×10.sup.5) PDI Comparison 0 5 101.9 132.11 2.52 28.2 Example 4 Comparison 0.7 5 111.3 131.73 2.11 20.1 Example 7-1 Comparison 2.1 5 104.0 131.30 2.13 25.9 Example 7-2 Comparison 3.5 5 72.8 131.34 2.08 23.8 Example 7-3 Example 15-1 0 5 145.6 132.16 2.76 30.1 Example 18-1 0.7 5 127.9 131.54 3.74 38.6 Example 18-2 2.1 5 124.8 131.41 3.45 50.4 Example 18-3 3.5 5 122.7 131.06 3.24 50.1 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.

(64) Example 8 and 9 are two step impregnation and total immersion respectively in different load method preparation of chrome vanadium catalyst in the same conditions of polymerization activity, visible by dipping the preparation of composite catalyst activity is higher.

(65) Cr—V catalyst is presented in table 6 catalysts and Phillips catalysts 1-hexene polymerization of vinyl results. Chrome vanadium double active center 1-hexene ethylene copolymerization activity presents the lower trend, combined with the result of ethylene homopolymerization before, showed that ethylene 1-hexene copolymerization activity are lower than the activity of ethylene homopolymerization. Phillips catalysts of ethylene 1-hexene copolymerization activity presents a slightly increased after the first reduce trend. Add 1-hexene, other chrome vanadium dual active center catalyst polymerization activity also declined.

(66) FIGS. 3 and 4, respectively, double active center for chrome vanadium catalyst, Phillips catalysts as well as the load vanadium oxide catalysts of ethylene homopolymer and ethylene with 1-hexene GPC chromatogram of the copolymer product comparison.

(67) (5) Comparison of Hydrogen

(68) TABLE-US-00007 TABLE 7 Comparison of hydrogen activity (kg PE/ mol Cr M.sub.w Example H.sub.2 Al/Cr h) T.sub.m (° C.) (×10.sup.5) PDI Comparison 0 5 101.9 132.11 2.52 28.2 Example 4 Comparison 10 5 110.2 131.79 2.19 28.4 Example 8 Example 15-1 0 5 145.6 132.16 2.76 30.1 Example 19 10 5 157.0 131.66 2.41 29.6 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.

(69) Table 7 shows, ethylene homopolymerization of different catalyst activity is lower than without the presence of hydrogen and the molecular weight of polyethylene and melting point is lower, that the hydrogen have the effect of chain transfer agent led to a decline in its molecular weight and melting point.

Example 22

(70) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 1%. After being continuously stirred for 4 h, heated to 80° C. and dried in vacuum 2 h and in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 23

(71) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 24

(72) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 5%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 25

(73) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 26

(74) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 5%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate and alkali type chromium acetate at 40° C., enabled the V and Cr loading (based on the mass of V and Cr) to be 0.24% and 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 27

(75) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.96%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 28

(76) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of vanadyl oxalate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of CrO.sub.3, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 29

(77) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.16%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 30

(78) 10 g of sodium silicate was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 31

(79) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of Titanium isopropoxide at 40° C. with pH=2˜3, enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 32

(80) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 5%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then it was impregnated in an aqueous solution of ammonium metavanadate at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 33

(81) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a aqueous solution of titanium sulfate and vanadyl oxalate, enabled the Ti and V loading (based on the mass of Ti and V) to be 5% and 0.24%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti and V modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of alkali type chromium acetate at 40° C., enabled the Cr loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 34

(82) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a aqueous solution of titanium sulfate and CrO.sub.3, enabled the Ti and Cr loading (based on the mass of Ti and Cr) to be 5% and 0.5%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti and Cr was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti and Cr modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of fluoride ammonium vanadate acetate at 40° C., enabled the V loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 35

(83) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of titanium sulfate and vanadyl oxalate, enabled the Ti, V and Cr loading (based on the mass of Ti, V and Cr) to be 5%, 0.24% and 0.5%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 36

(84) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate, enabled the Ti loading (based on the mass of Ti) to be 3%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel carrier supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then it was impregnated in an aqueous solution of (acac).sub.2V at 40° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then used organometallic co-catalysts MAO to pre-reduction the catalyst precursor, the concentration of co-catalyst was 1.0 mmol/mL. Finally drying at 100° C. for 4 h, the drying is conducted under an inert gas atmosphere.

Example 37

(85) 160 mg of the catalyst in Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 38

(86) 160 mg of the catalyst in Example 23 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5, 10, 15, 20, 30 (Example 38-1, 38-2, 38-3, 38-4, 38-5). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 39

(87) 160 mg of the catalyst in Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 40

(88) 160 mg of the catalyst in Example 25 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 41

(89) 160 mg of the catalyst in Example 26 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 42

(90) 160 mg of the catalyst in Example 27 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 43

(91) 160 mg of the catalyst in Example 28 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 44

(92) 160 mg of the catalyst in Example 29 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 45

(93) 160 mg of the catalyst in Example 30 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 46

(94) 160 mg of the catalyst in Example 31 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 47

(95) 160 mg of the catalyst in Example 32 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 48

(96) 160 mg of the catalyst in Example 33 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 49

(97) 160 mg of the catalyst in Example 34 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 50

(98) 160 mg of the catalyst in Example 35 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 51

(99) 160 mg of the catalyst in Example 36 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration, Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 52

(100) 160 mg of the catalyst in Example 23 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. The amount of 1-hexene was respectively 1.4 mL, 2.8 mL, and 4.2 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 2 vol % (Example 52-1), 4 vol % (Example 52-2) and 6 vol % (Example 52-3). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 53

(101) 160 mg of the catalyst in Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. The amount of 1-hexene was respectively 1.4 mL, 2.8 mL, and 4.2 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 2 vol % (Example 53-1), 4 vol % (Example 53-2) and 6 vol % (Example 53-3). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 54

(102) 160 mg of the catalyst in Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Example 54-1, 54-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 55

(103) 160 mg of the catalyst in Example 23 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Example 55-1, 55-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 56

(104) 160 mg of the catalyst in Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Example 56-1, 56-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 57

(105) 160 mg of the catalyst in Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 55° C. and 70° C. for 1 h (Example 57-1, 57-2), a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 58

(106) 160 mg of the catalyst in Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 59

(107) 160 mg of the catalyst in Example 23 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent respectively. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 60

(108) 160 mg of the catalyst in Example 28 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 14

(109) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium metavanadate at 45° C., enabled the vanadium loading (based on the mass of V) to be 0.24%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed in 450° C. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 0.5%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Comparison Example 15

(110) 20 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a n-hexane solution of tetra-n-butyl titanate at 40° C., enabled the Ti loading (based on the mass of Ti) to be 5%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 5. Then 10 g of it was impregnated in an aqueous solution of ammonium dichromate, enabled the Cr loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then another 10 g of it was impregnated in an aqueous solution of vanadyl oxalate, enabled the V loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Mix the catalyst produced above as the Cr/V=2:1 to obtain a mixture catalyst.

Comparison Example 16

(111) 160 mg of the catalyst in Comparison Example 14 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5, 10, 15, 20, 30 (Comparison Example 16-1, 16-2, 16-3, 16-4, 16-5). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 17

(112) 160 mg of the catalyst in Comparison Example 14 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 18

(113) 160 mg of the catalyst in Comparison Example 1 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. The amount of 1-hexene was respectively 1.4 mL, 2.8 mL, and 4.2 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 2 vol % (Comparison Example 18-1), 4 vol % (Comparison Example 18-2) and 6 vol % (Comparison Example 18-3). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 19

(114) 160 mg of the catalyst in Comparison Example 14 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Comparison Example 19-1, 19-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 20

(115) 160 mg of the catalyst in Comparison Example 14 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 55° C. and 70° C. for 1 h (Comparison Example 20-1, 20-2), a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 21

(116) 160 mg of the catalyst in Comparison Example 15 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

(117) TABLE-US-00008 TABLE 8 Polymerization activities of examples Activity Example (kg.sub.PE/mol Cr or V h) Example 37 203.86 Example 38-1 227.08 Example 38-2 174.87 Example 38-3 134.07 Example 38-4 133.86 Example 38-5 104.22 Example 39 232.33 Example 40 193.75 Example 41 198.80 Example 42 139.73 Example 43 233.68 Example 44 201.69 Example 45 192.57 Example 46 223.80 Example 47 186.21 Example 48 102.49 Example 49 98.26 Example 50 91.12 Example 51 142.06 Example 52-1 195.79 Example 52-2 188.80 Example 52-3 157.81 Example 53-1 199.36 Example 53-2 170.30 Example 53-3 102.53 Example 54-1 195.83 Example 54-2 190.65 Example 55-1 226.59 Example 55-2 187.13 Example 56-1 228.74 Example 56-2 143.23 Example 57-1 543.23 Example 57-2 413.74 Example 58 185.10 Example 58 80.82 Example 60 156.18 Comparison Example 16-1 207.97 Comparison Example 16-2 176.94 Comparison Example 16-3 141.21 Comparison Example 16-4 117.44 Comparison Example 16-5 135.16 Comparison Example 17 188.88 Comparison Example 18-1 189.73 Comparison Example 18-2 172.88 Comparison Example 18-3 102.62 Comparison Example 19-1 207.45 Comparison Example 19-2 220.52 Comparison Example 20-1 585.73 Comparison Example 20-2 442.83 Comparison Example 21 163.58
(1) Comparison of Different Amount of Cocatalyst

(118) TABLE-US-00009 TABLE 9 Comparison of different amount of cocatalyst in ethylene homopolymerization activity (kg PE/ T.sub.m M.sub.w Example Al/Cr mol Cr h) (° C.) (×10.sup.5) PDI Example 38-1 5 227.08 131.58 6.04 39.90 Example 38-2 10 174.87 132.80 6.13 28.34 Example 38-3 15 134.07 133.13 8.34 44.31 Example 38-4 20 133.86 133.74 8.55 48.51 Example 38-5 30 104.22 133.71 8.28 14.68 Comparison 5 207.97 131.11 4.90 43.67 Example 16-1 Comparison 10 176.94 132.93 6.41 36.71 Example 16-2 Comparison 15 141.21 133.24 7.03 20.73 Example 16-3 Comparison 20 117.44 133.72 7.82 18.14 Example 16-4 Comparison 30 135.16 133.69 7.37 14.60 Example 16-5 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; polymerization temperature = 85° C.; n-heptane = 70 mL; Cr = 0.5% (wt), co-catalyst = TIBA.

(119) From table 9 shows that in three isobutyl aluminum (TIBA) as cocatalyst conditions (16 example and contrast 38 cases), with the help of catalyst increasing, chrome vanadium titanium dioxide modified load type double active center type chrome vanadium catalyst and unmodified load double active center of the activity of catalyst in ethylene homopolymerization downward trend, while the polymer molecular weight showed a trend of reducing the rise, then required to get the polymer molecular weight, the dosage of the catalyst promoter is an appropriate value or range. Using other except TiBA cocatalyst in a similar rule.

(120) (2) Comparison of Different Cocatalyst

(121) TABLE-US-00010 TABLE 10 Comparison of different cocatalyst in ethylene homopolymerization activity (kg PE/ T.sub.m M.sub.w Example co-catalyst mol Cr h) (° C.) (×10.sup.5) PDI Example 39 TIBA 232.33 131.58 4.62 46.04 Example 58 TEA 185.10 132.02 3.14 10.61 Comparison TIBA 207.97 131.11 4.90 43.67 Example 16-1 Comparison TEA 188.88 132.09 2.54 11.21 Example 17 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; polymerization temperature = 85° C.; n-heptane = 70 mL; Cr = 0.5% (wt);

(122) Table 10 different cocatalyst is presented for titanium dioxide modified and unmodified load type chrome vanadium double metal oxide catalysts for catalytic active sites of ethylene homopolymerization activity (Example 39, 58 and Comparison Example 16-1, 17). Visible, use the three isobutyl aluminum (TiBA) as cocatalyst, two kinds of catalyst activity were significantly higher than that of using triethyl aluminium (TEA) as catalyst promoter activity of ethylene homopolymerization. Further through the analysis of the above product polyethylene, under different cocatalyst is the melting point of polyethylene products have similar, but its very different molecular weight and molecular weight distribution, showed the cocatalyst to the center of the catalyst activity after reduction degree and reduction of distribution has great influence.

(123) (3) Comparison of Temperature

(124) TABLE-US-00011 TABLE 11 Comparison of temperature activity (kg PE/ T.sub.m M.sub.w Example temp. mol Cr h) (° C.) (×10.sup.5) PDI Example 57-1 55 543.23 131.66 7.28 27.19 Example 57-2 70 413.74 131.68 4.73 41.38 Example 39 85 232.33 131.58 4.62 46.04 Comparison 55 585.73 131.79 6.00 36.69 Example 20-1 Comparison 70 442.83 130.77 5.14 25.24 Example 20-2 Comparison 85 207.97 131.11 4.90 43.67 Example 16-1 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt); co-catalyst = TIBA.

(125) Table 11 for different polymerization temperature of titanium dioxide modified and unmodified double active center load type chrome vanadium catalysts of ethylene homopolymerization activity (Example 39, 57 and Comparison Example 16-1, 20). In 55° C. to 85° C. of polymerization temperature range, the catalyst with the highest activity at 55° C., with the increase of temperature reduction catalyst polymerization activity, the minimum activity at 85° C. Under different temperature of the melting point of polyethylene products have similar, its molecular weight with the increase of polymerization temperature decrease trend, chain transfer reaction shows polymerization temperature on polymerization more advantageous.

(126) (4) Comparison of Different Dosage of 1-Hexene

(127) TABLE-US-00012 TABLE 12 Comparison of different dosage of 1-hexene activity (kg PE/ T.sub.m M.sub.w Example 1-hexene mol Cr h) (° C.) (×10.sup.5) PDI Example 38-1 0 227.08 132.80 6.04 39.90 Example 52-1 1.4 195.79 132.40 6.33 36.53 Example 52-2 2.8 188.80 132.09 5.86 42.64 Example 52-3 4.2 157.81 131.98 5.95 46.01 Example 39 0 232.33 131.58 4.62 46.04 Example 53-1 1.4 199.36 131.85 6.44 44.21 Example 53-2 2.8 170.30 131.93 5.45 37.43 Example 53-3 4.2 102.53 131.83 4.83 48.25 Comparison 0 207.97 131.11 4.90 43.67 Example 16-1 Comparison 1.4 189.73 131.86 3.10 10.95 Example 18-1 Comparison 2.8 172.88 131.76 5.17 38.30 Example 18-2 Comparison 4.2 102.62 131.15 4.62 47.61 Example 18-3 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.
Titanium dioxide modified load model is presented in table 12 chrome vanadium double active center of the ethylene/1-hexene catalyzed polymerization activity (Example 38-1, 39, 52, 53, and Comparison Example 16-1, 18). With the increase of dosage of 1-hexene, chrome vanadium titanium dioxide modified load type double active center/1-hexene ethylene copolymerization activity presents the lower trend, combined with the result of ethylene homopolymerization before, showed that ethylene/1-hexene copolymerization activity are lower than the activity of ethylene homopolymerization.
(5) Comparison of Different Preparation of Catalyst

(128) TABLE-US-00013 TABLE 13 Comparison of different preparation of catalyst activity (kg PE/ T.sub.m M.sub.w Example cocat. mol Cr h) (° C.) (×10.sup.5) PDI Example 39 TIBA 232.33 131.58 4.62 46.04 Example 58 TEA 185.10 132.02 3.14 10.61 Example 43 TIBA 233.68 131.86 4.28 43.19 Example 60 TEA 156.18 132.31 2.93 19.32 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt)

(129) Table 13 is compared the two kinds of titanium type (impregnation method and sol-gel method) preparation of titanium dioxide modified double active center load type chrome vanadium catalyst of catalytic activity of ethylene homopolymerization. Implementation example of 39, 58 of titanium dioxide prepared catalyst is impregnation method modified silica gel as the carrier, Example 43, 60 of catalyst is based on sol gel method of titanium dioxide modified silica gel as carrier. From the table 13 shows, when to TIBA as cocatalyst, two types of titanium is introduced into the preparation of catalyst for ethylene homopolymerization activity were small; But, when with TEA as cocatalyst, impregnation method for the modification of the load on the chrome vanadium titanium dioxide double ethylene homopolymerization of active center catalyst activity significantly higher than that of using sol-gel method homopolymerization activity of the catalyst.

(130) TABLE-US-00014 TABLE 14 Comparison of different preparation of catalyst activity (kg PE/ T.sub.m M.sub.w Example mol Cr h) (° C.) (×10.sup.5) PDI Example 39 232.33 131.58 4.62 46.04 Example 41 198.80 131.12 4.37 43.86 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt)

(131) Table 14 is compared the two chrome vanadium load modes (chrome vanadium by dipping on the modification of TiO.sub.2 carrier and chrome vanadium were impregnated in the modification of TiO.sub.2 carrier) preparation of titanium dioxide modified double active center type load chrome vanadium catalyst of catalytic activity of ethylene homopolymerization. Visible, use the chrome vanadium titanium dioxide modified prepared step by step impregnation method of double active center load type chrome vanadium catalyst ethylene homopolymerization activity is higher than chrome vanadium total immersion of the catalyst prepared by the homopolymerization of activity.

(132) (6) Comparison of Dosage of TiO.sub.2

(133) TABLE-US-00015 TABLE 15 Comparison of dosage of TiO.sub.2 activity (kg PE/ T.sub.m M.sub.w Example Al/Cr mol Cr h) (° C.) (×10.sup.5) PDI Comparison 5 207.97 131.11 4.90 43.67 Example 16-1 Example 37 5 203.86 131.86 6.81 44.15 Example 38-1 5 227.08 132.80 6.04 39.90 Example 39 5 232.33 131.58 4.62 46.04 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), co-catalyst = TIBA.

(134) Given in table 15 different titanium dioxide content of titanium dioxide modified load type double active center chrome vanadium oxide catalyst polymerization reactivity (Example 37, 38-1, 39 and Comparison Example 16-1). Implementation Example 39 were molecular weight polyethylene products than Comparison Example 16-1 the low molecular weight polyethylene products; Example 37 and practiced by Example 38-1 heaviness in the preparation of polyethylene products molecular weight than Comparison Example 16-1 high molecular weight polyethylene products. This shows that the titanium dioxide is introduced into the catalytic system affect the activity of catalyst center. In addition, the product of PDI is around Example 40, there is no significant change.

(135) (7) Comparison of Hydrogen

(136) TABLE-US-00016 TABLE 16 Comparison of hydrogen activity (kg PE/ T.sub.m M.sub.w Example H.sub.2 mol Cr h) (° C.) (×10.sup.5) PDI Example 37 0 203.86 131.86 6.80 44.15 Example 54-1 10 195.83 131.70 5.01 54.72 Example 54-2 20 190.65 132.29 3.52 14.92 Example 38-1 0 227.08 132.80 6.03 39.90 Example 55-1 10 226.59 132.09 4.96 21.84 Example 55-2 20 187.13 132.22 3.03 35.77 Example 39 0 232.33 131.58 4.62 46.04 Example 56-1 10 228.74 132.03 3.52 14.92 Example 56-2 20 143.23 131.91 3.44 24.76 Comparison 0 207.97 131.11 4.90 43.67 Example 16-1 Comparison 10 207.45 131.18 4.16 15.46 Example 19-1 Comparison 20 220.52 131.20 3.39 12.56 Example 19-2 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt); co-catalyst = TIBA.

(137) The load of different titanium dioxide modified double active center type chrome vanadium oxide catalysts of the effects of hydrogen transfer reaction such as shown in table 16 (Example 37, 38-1, 39, 54, 55, 56 and Comparison Example 16-1, 19). Visible, hydrogen after chrome vanadium titanium dioxide modified load type double active center of catalysts of ethylene homopolymerization activity than hydrogen does not exist under the condition of lower, and the molecular weight of polyethylene greatly decreased, and that the hydrogen plays a significant role of chain transfer agent to lower molecular weight polyethylene.

Example 61

(138) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of ammonium metavanadate, enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 62

(139) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 0.75%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of ammonium metavanadate, enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 63

(140) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of ammonium metavanadate and alkali type chromium acetate, enabled the V and Cr loading (based on the mass of V and Cr) to be 0.48% and 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 64

(141) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of vanadyl oxalate, enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of CrO.sub.3, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 65

(142) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then it was impregnated in an aqueous solution of ammonium metavanadate, enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 66

(143) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate and vanadyl oxalate, enabled the F and V loading (based on the mass of F and V) to be 1.5% and 0.48%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the Ti was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F and V modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of alkali type chromium acetate at 40° C., enabled the Cr loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 67

(144) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in a aqueous solution of NH.sub.4F and CrO.sub.3, enabled the F and Cr loading (based on the mass of F and Cr) to be 1.5% and 1%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, the silica gel support supporting the F and Cr was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a Ti and Cr modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of vanadyl oxalate at 40° C., enabled the V loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 68

(145) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, alkali type chromium acetate and ammonium metavanadate, enabled the F, V and Cr loading (based on the mass of F, V and Cr) to be 1.5%, 0.48% and 1%. After being continuously stirred for 4 h, heated to 80° C. and dried in air for 8 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Example 69

(146) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then it was impregnated in an aqueous solution of (acac).sub.2V, enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. After that it was impregnated in an aqueous solution of CrO.sub.3, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then used organometallic co-catalysts MAO to pre-reduction the catalyst precursor, the concentration of co-catalyst was 1.0 mmol/mL. Finally drying at 100° C. for 4 h, the drying is conducted under an inert gas atmosphere.

Example 70

(147) 160 mg of the catalyst in Example 61 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 71

(148) 160 mg of the catalyst in Example 62 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 72

(149) 160 mg of the catalyst in Example 63 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 73

(150) 160 mg of the catalyst in Example 64 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 74

(151) 160 mg of the catalyst in Example 65 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 75

(152) 160 mg of the catalyst in Example 66 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 76

(153) 160 mg of the catalyst in Example 68 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5, 5, 10, 15, 20, (Example 76-1, 76-2, 76-3, 76-4, 76-5). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 77

(154) 160 mg of the catalyst in Example 67 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 78

(155) 160 mg of the catalyst in Example 69 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 79

(156) 160 mg of the catalyst in Example 67 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. The amount of 1-hexene was respectively 0.7 mL, 2.1 mL, and 3.5 mL, i.e. the volume ratio of 1-hexene and the solvent used for polymerization being 21 vol % (Example 79-1), 3 vol % (Example 79-2) and 5 vol % (Example 79-3). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 80

(157) 160 mg of the catalyst in Example 67 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Example 80-1, 80-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 81

(158) 160 mg of the catalyst in Example 62 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Example 81-1, 81-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 82

(159) 160 mg of the catalyst in Example 63 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Example 82-1, 82-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 83

(160) 160 mg of the catalyst in Example 67 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=10. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 45° C. and 65° C. for 1 h (Example 83-1, 83-2), a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 84

(161) 160 mg of the catalyst in Example 63 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 85

(162) 160 mg of the catalyst in Example 62 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Example 86

(163) 160 mg of the catalyst in Example 67 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 22

(164) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium metavanadate at 45° C., enabled the vanadium loading (based on the mass of V) to be 0.48%. After being continuously stirred for 5 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed in 450° C. Finally, it was naturally cooled down under the protection of nitrogen gas to obtain a vanadium supported catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 1. Then it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Comparison Example 23

(165) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. After that it was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Comparison Example 24

(166) 10 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of alkali type chromium acetate, enabled the chromium loading (based on the mass of Cr) to be 1%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 4 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas.

Comparison Example 25

(167) 20 g of silica gel (having a pore volume of 1.5˜1.7 cm.sup.3/g and a surface area of 250˜300 m.sup.2/g) was impregnated in an aqueous solution of ammonium fluorosilicate, enabled the F loading (based on the mass of F) to be 1.5%. After being continuously stirred for 4 h, heated to 80° C. for 8 h, the silica gel support supporting the F was high-temperature calcined in a fluidized bed. Then, the silica gel was naturally cooled down under the protection of nitrogen gas to obtain a F modified catalyst precursor. The high temperature calcining and then cooling processes above are shown in FIG. 8. Then 10 g of it was impregnated in an aqueous solution of ammonium dichromate, enabled the Cr loading (based on the mass of Cr) to be 2%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Then another 10 g of it was impregnated in an aqueous solution of vanadyl oxalate, enabled the V loading (based on the mass of V) to be 0.96%. After being continuously stirred for 4 h, heated to 120° C. and dried in air for 6 h, it was high-temperature calcined in a fluidized bed. Finally, it was naturally cooled down under the protection of nitrogen gas. Mix the catalyst produced above as the Cr/V=2:1 to obtain a mixture catalyst.

Comparison Example 26

(168) 160 mg of the catalyst in Comparison Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5, 5, 10, 15, 20 (Comparison Example 26-1, 26-2, 26-3, 26-4, 26-5). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 27

(169) 160 mg of the catalyst in Comparison Example 23 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5, 5, 10, 15, 20 (Comparison Example 27-1, 27-2, 27-3, 27-4, 27-5). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 28

(170) 160 mg of the catalyst in Comparison Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). The polymerization temperature was maintained at 85° C. Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5, 5, 10, 15, 20 (Comparison Example 28-1, 28-2, 28-3, 28-4, 28-5). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 29

(171) 160 mg of the catalyst in Comparison Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. The amount of 1-hexene was respectively 0.7 mL and 2.1 mL, the volume ratio of 1-hexene and the solvent used for polymerization being 1 vol % (Comparison Example 29-1) and 3 vol % (Comparison Example 29-2). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 30

(172) 160 mg of the catalyst in Comparison Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated (100° C.) under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, a refined hexene treated by dehydration and deoxidation as comonomer and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. The amount of 1-hexene was respectively 0.7 mL and 2.1 mL, the volume ratio of 1-hexene and the solvent used for polymerization being 1 vol % (Comparison Example 30˜1) and 3 vol % (Comparison Example 30-2). Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 31

(173) 160 mg of the catalyst in Comparison Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Comparison Example 31-1, 31-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 32

(174) 160 mg of the catalyst in Comparison Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent, 10 mL and 20 mL hydrogen (Comparison Example 32-1, 32-2) and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 33

(175) 160 mg of the catalyst in Comparison Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 45° C. and 65° C. for 1 h (Comparison Example 33-1, 33-2), a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 34

(176) 160 mg of the catalyst in Comparison Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 ml of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 45° C. and 65° C. for 1 h (Comparison Example 34-1, 34-2), a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 35

(177) 160 mg of the catalyst in Comparison Example 22 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 36

(178) 160 mg of the catalyst in Comparison Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TEA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

Comparison Example 37

(179) 160 mg of the catalyst in Comparison Example 24 was weighed for the polymerization respectively. The polymerization reaction kettle was firstly heated under vacuum, and then replaced with highly pure nitrogen, which was repeated for three times. Then a small amount of monomeric ethylene was used to replace once. Finally, the reaction kettle was filled with ethylene to a slight positive pressure (0.12 MPa). Into the reaction kettle were added in turn about 70 mL of a refined heptane treated by dehydration and deoxidation as solvent and TIBA as co-catalyst respectively, wherein the co-catalyst had a concentration of 1.0 mmol/mL (n-hexane solution) and Al/Cr (molar ratio)=2.5. Finally the pressure of ethylene in the kettle was raised to 0.15 MPa and the catalyst was added to start the polymerization. The instantaneous consumption of monomeric ethylene was on-line collected (by the high-precision ethylene mass flow meter connecting with a computer) during the reaction and recorded by the computer. After the reaction was conducted at 85° C. for 1 h, a mixed solution of hydrochloric acid/ethanol was added to terminate the reaction, and the polymer was vacuum dried, weighed and analyzed.

(180) TABLE-US-00017 TABLE 17 Polymerization activities of examples Activity (kg.sub.PE/mol Example Cr or V h) Example 70 90.5 Example 71 71.2 Example 72 91.8 Example 73 89.0 Example 74 85.2 Example 75 93.5 Example 76-1 105.1 Example 76-2 62.6 Example 76-3 55.0 Example 76-4 50.6 Example 76-5 44.3 Example 77 78.6 Example 78 67.5 Example 79-1 73.9 Example 19-2 61.3 Example 80-1 98.6 Example 80-2 83.4 Example 81-1 62.3 Example 81-2 51.4 Example 82-1 81.2 Example 82-2 75.4 Example 83-1 315.2 Example 83-2 243.7 Example 84 78.5 Example 85 31.6 Example 86 93.2 Comparison Example 26-1 149.0 Comparison Example 26-2 114.4 Comparison Example 26-3 87.5 Comparison Example 26-4 83.4 Comparison Example 26-5 71.4 Comparison Example 27-1 96.5 Comparison Example 27-2 51.2 Comparison Example 27-3 39.4 Comparison Example 27-4 32.3 Comparison Example 27-5 22.8 Comparison Example 28-1 131.6 Comparison Example 28-2 100.3 Comparison Example 28-3 77.7 Comparison Example 28-4 64.1 Comparison Example 28-5 66.3 Comparison Example 29-1 114.3 Comparison Example 29-2 97.3 Comparison Example 30-1 104.5 Comparison Example 30-2 84.9 Comparison Example 31-1 136.6 Comparison Example 31-2 135.1 Comparison Example 32-1 105.6 Comparison Example 32-2 105.0 Comparison Example 33-1 140.3 Comparison Example 33-2 226.5 Comparison Example 34-1 162.7 Comparison Example 34-2 265.8 Comparison Example 35 99.1 Comparison Example 36 121.9
(1) Comparison of Different Amount of Cocatalyst

(181) TABLE-US-00018 TABLE 18 Comparison of different amount of cocatalyst in ethylene homopolymerization activity (kg PE/ T.sub.m M.sub.w Example Al/Cr mol Cr h) (° C.) (×10.sup.5) PDI Example 76-1 2.5 105.1 131.2 5.21 22.7 Example 76-2 5 62.6 131.9 6.23 25.4 Example 76-3 10 55.0 132.4 7.98 34.3 Example 76-4 15 50.6 132.7 7.15 28.5 Example 76-5 20 44.3 132.5 6.38 30.8 Comparison 2.5 149.0 131.2 4.40 25.5 Example 26-1 Comparison 5 114.4 131.9 4.79 26.1 Example 26-2 Comparison 10 87.5 132.2 7.13 29.7 Example 26-3 Comparison 15 83.4 131.7 6.42 28.5 Example 26-4 Comparison 20 71.4 131.3 6.17 25.6 Example 26-5 Comparison 2.5 96.5 131.0 4.78 22.3 Example 27-1 Comparison 5 51.2 131.9 6.31 21.7 Example 27-2 Comparison 10 39.4 132.2 7.13 28.9 Example 27-3 Comparison 15 32.3 131.8 7.02 26.1 Example 27-4 Comparison 20 22.8 132.0 5.97 24.7 Example 27-5 Comparison 2.5 131.6 131.1 3.28 23.8 Example 28-1 Comparison 5 100.3 131.3 5.41 22.1 Example 28-2 Comparison 10 77.7 131.9 6.33 27.3 Example 28-3 Comparison 15 64.1 131.7 5.82 29.4 Example 28-4 Comparison 20 66.3 131.5 5.37 25.6 Example 28-5 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; polymerization temperature = 85° C.; n-heptane = 70 mL; Cr = 0.5% (wt), co-catalyst = TIBA.

(182) From FIG. 8 shows, in the TIBA as cocatalyst conditions (Example 76-1 76-2 76-3 76-4 76-5 and Comparison Example 26-1 26-2 26-3 26˜4 26-5 27-1 27-2 27-3 27-4 27-5 28-1 28-2 28-3 28-4 28-5), with the help of catalyst increasing, fluorine of modified and unmodified load type chrome vanadium double active center metal oxide catalyst and fluorine modified phillips catalysts, unmodified phillips catalyst activity of ethylene homopolymerization presents the downward trend, while the polymer molecular weight showed a trend of reducing the rise, then required to get the polymer molecular weight, the dosage of the catalyst promoter is an appropriate value or range. Using other except TiBA cocatalyst in a similar rule.

(183) (2) Comparison of Different Cocatalyst

(184) TABLE-US-00019 TABLE 19 Comparison of different cocatalyst in ethylene homopolymerization activity (kg PE/ T.sub.m M.sub.w Example co-catalyst mol Cr h) (° C.) (×10.sup.5) PDI Example 76-1 TIBA 105.1 131.2 5.21 22.7 Example 86 TEA 93.2 131.3 2.25 23.3 Comparison TIBA 149.0 131.2 4.40 25.5 Example 26-1 Comparison TEA 99.1 132.1 2.69 15.6 Example 35 Comparison TIBA 131.6 131.1 3.28 23.8 Example 28-1 Comparison TEA 121.9 131.2 1.94 11.3 Example 36 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; polymerization temperature = 85° C.; n-heptane = 70 mL; Cr = 0.5% (wt);

(185) Given in table 19 different cocatalyst for fluoride load type of modified and unmodified chrome vanadium double active center metal oxide catalyst, unmodified ethylene homopolymerization phillips catalysts for catalytic activity (Example 76-1, 86, and Comparison Example 26-1, 35, 28-1, 36). Visible, use the TIBA as cocatalyst, two kinds of catalyst activity were significantly higher than that of using triethyl aluminium (TEA) as catalyst promoter activity of ethylene homopolymerization. Further through the analysis of the above product polyethylene, under different cocatalyst is the melting point of polyethylene products have similar, but its very different molecular weight and molecular weight distribution, showed the cocatalyst to the center of the catalyst activity after reduction degree and reduction of distribution has great influence.

(186) (3) Comparison of Temperature

(187) TABLE-US-00020 TABLE 20 Comparison of temperature activity temp. (kg PE/ T.sub.m M.sub.w Example (° C.) mol Cr h) (° C.) (×10.sup.5) PDI Example 83-1 45 315.2 131.7 10.12 21.5 Example 83-2 65 243.7 130.8 9.89 20.9 Example 76-1 85 105.1 131.2 9.01 22.7 Comparison 45 140.3 134.1 6.36 21.9 Example 33-1 Comparison 65 226.5 131.1 5.90 22.9 Example 33-2 Comparison 85 149.0 131.2 5.76 25.5 Example 26-1 Comparison 45 162.7 133.5 6.18 20.6 Example 34-1 Comparison 65 265.8 130.6 4.22 21.8 Example 34-2 Comparison 85 131.6 131.1 3.47 23.8 Example 28-1 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt); co-catalyst = TIBA.

(188) Table 20 is different polymerization temperature of fluorine of modified and unmodified load type chrome vanadium double active center metal oxide catalyst, unmodified phillips catalysts of ethylene homopolymerization activity (Example 83-1 83-2 76-1 and Comparison Example 33-1 33-2 26-1 34-1 34-2 28-1). Under different temperature of the melting point of polyethylene products have similar, fluorine modified load type chrome vanadium double active center metal oxide catalysts in the rise of its molecular weight as the polymerization temperature trends, chain transfer reaction shows polymerization temperature on polymerization more advantageous.

(189) (4) Comparison of Different Dosage of 1-Hexene

(190) TABLE-US-00021 TABLE 21 Comparison of different dosage of 1-hexene activity (kg PE/ T.sub.m M.sub.w Example 1-hexene mol Cr h) (° C.) (×10.sup.5) PDI Example 76-1 0 105.1 131.2 5.21 22.7 Example 79-1 0.7 73.9 131.7 4.57 20.3 Example 79-2 2.1 61.3 131.5 3.47 16.9 Comparison 0 149.0 131.2 4.40 25.5 Example 26-1 Comparison 0.7 114.3 131.8 4.21 24.9 Example 29-1 Comparison 2.1 97.3 131.6 4.01 25.4 Example 29-2 Comparison 0 131.6 131.1 3.28 23.8 Example 28-1 Comparison 0.7 104.5 132.2 3.02 20.8 Example 30-1 Comparison 2.1 84.9 131.9 2.83 18.0 Example 30-2 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt), V = 0.24% (wt); co-catalyst = TIBA.
Fluorine is presented in table 21 of modified and unmodified load type chrome vanadium double active center metal oxide catalyst, unmodified phillips, the ethylene/1-hexene catalyzed polymerization activity (Example 76-1 79-1 79-2, and Comparison Example 26-1 29-1 29-2 28-1 30-1 30-2). With the increase of dosage of 1-hexene, fluorine modified load type chrome vanadium double active center metal oxide catalysts of ethylene/1-hexene copolymerization activity present a lower trend, combined with the result of ethylene homopolymerization before, showed that ethylene/1-hexene copolymerization activity were lower than the activity of ethylene homopolymerization. With the increase of dosage of 1-hexene polymer molecular weight falling.
(7) Comparison of Hydrogen

(191) TABLE-US-00022 TABLE 16 Comparison of hydrogen activity (kg PE/ T.sub.m M.sub.w Example H.sub.2 mol Cr h) (° C.) (×10.sup.5) PDI Example 76-1 0 105.1 131.2 5.21 22.7 Example 80-1 10 98.6 131.4 3.84 27.4 Example 80-2 20 83.4 131.1 3.05 28.5 Comparison 0 149.0 131.2 4.40 25.5 Example 26-1 Comparison 10 136.6 131.2 2.90 18.9 Example 31-1 Comparison 20 135.1 131.1 2.63 17.5 Example 31-2 Comparison 0 131.6 131.1 3.28 23.8 Example 28-1 Comparison 10 105.6 131.1 2.04 14.7 Example 32-1 Comparison 20 105.0 131.1 1.95 15.5 Example 32-2 Polymerization conditions: ethylene pressure = 0.15 MPa; polymerization time = 1 hr; n-heptane = 70 mL; Cr = 0.5% (wt); co-catalyst = TIBA.

(192) Fluorine of modified and unmodified load type chrome vanadium double active center metal oxide catalyst, unmodified phillips catalyst of the effects of hydrogen transfer reaction such as shown in table 22 (Example 76-1 80-1 80-2 and Comparison Example 26-1 31-1 31-2 28-1 32-1 33-2). After the visible, hydrogen fluoride modified double active center load type chrome vanadium catalysts of ethylene homopolymerization activity than hydrogen does not exist under the condition of lower, and significantly lower molecular weight polyethylene, illustrate the hydrogen plays a significant role of chain transfer agent to lower molecular weight polyethylene.