Olefin coordination polymerization catalyst and use thereof

Abstract

The present invention provides an olefin coordination polymerization catalyst and use thereof. The composition of the raw materials of the olefin coordination polymerization catalyst comprises: a main catalyst and a cocatalyst, wherein a molar ratio of the transition metal halide in the main catalyst to the cocatalyst is 1:10-500; and the composition of the raw materials of the main catalyst comprises a magnesium compound, a transition metal halide, an alcohol having 2 to 15 carbon atoms, and a star-shaped organosiloxane compound in a molar ratio of 1:1-40:0.01-10:0.001-10; and the cocatalyst comprises an organoaluminum compound. The above olefin coordination polymerization catalyst is used as a catalyst for ethylene polymerization, propylene polymerization, and copolymerization of ethylene or propylene with an -olefin. The olefin polymerization catalyst of the present invention has good catalytic activity.

Claims

1. An olefin coordination polymerization catalyst, characterized in that the composition of the raw materials of the olefin coordination polymerization catalyst comprises: a solid main catalyst and a cocatalyst, wherein a molar ratio of the transition metal halide in the solid main catalyst to the cocatalyst is 1: 10-500; the composition of the raw materials of the solid main catalyst comprises a magnesium compound, a transition metal halide, an alcohol having 2 to 15 carbon atoms, and a star-shaped organosiloxane compound in a molar ratio of 1:1-40:0.01-10:0.001-10; the cocatalyst comprises an organoaluminum compound; the star-shaped organosiloxane compound is at least one selected from the group consisting of the compounds of the Formula (I): ##STR00006## wherein y, x and L are integers selected from 0, 1-15; M is Si; R.sub.1, R.sub.2, and R.sub.3 are organic groups, present simultaneously or not simultaneously, selected from H, C.sub.1-C.sub.20 aliphatic hydrocarbyl, C.sub.1-C.sub.20 alkoxy, C.sub.3-C.sub.20 alicyclic group, C.sub.3-C.sub.20 alicyclic alkoxy, C.sub.6-C.sub.20 aryloxy, or C.sub.6-C.sub.20 aromatic hydrocarbyl; R.sub.4, R.sub.5, and R.sub.6 are organic groups, present simultaneously or not simultaneously, selected from H, C.sub.1-C.sub.20 aliphatic hydrocarbyl, C.sub.1-C.sub.20 alkoxy, C.sub.3-C.sub.20 alicyclic group, C.sub.3-C.sub.20 alicyclic alkoxy, C.sub.6-C.sub.20 aryloxy, or C.sub.6-C.sub.20 aromatic hydrocarbyl; R.sub.7, R.sub.8, and R.sub.9 are organic groups, present simultaneously or not simultaneously, selected from H, C.sub.1-C.sub.20 aliphatic hydrocarbyl, C.sub.1-C.sub.20 alkoxy, C.sub.3-C.sub.20 alicyclic group, C.sub.3-C.sub.20 alicyclic alkoxy, C.sub.6-C.sub.20 aryloxy, or C.sub.6-C.sub.20 aromatic hydrocarbyl, wherein the solid main catalyst of the olefin coordination polymerization catalyst is prepared by the method comprising: dispersing the magnesium compound in an inert organic solvent, into which an alcohol having 2-15 carbon atoms is added, and stirring at 90 C. to 150 C. for 1 hour-5 hours; lowering the temperature to 30 C. to 80 C., and adding the star-shaped organosiloxane compound, and carrying out the reaction for 0.5 hour-3 hours to obtain a mixture; contacting the mixture with the transition metal halide at 25 C. to 30 C., reacting at 25 C. to 30 C. for 0.5 h-5 hours, heating to 50 C. to 120 C. in 2 hours-8 hours, and reacting for 0.5 h-5 hours; washing the product with toluene or n-hexane, filtering and drying under vacuum at 40 C. to 90 C. for 0.5 h-5 hours to obtain the solid main catalyst of the olefin coordination polymerization catalyst.

2. The olefin coordination polymerization catalyst according to claim 1, wherein the star-shaped organosiloxane compound is at least one selected from the compounds represented by the following structural formulae: ##STR00007## ##STR00008## ##STR00009##

3. The olefin coordination polymerization catalyst according to claim 1, wherein the magnesium compound is at least one selected from compounds of formula Mg(R).sub.aX.sub.b, wherein R is selected from C.sub.1-C.sub.20 aliphatic hydrocarbyl, C.sub.1-C.sub.20 aliphatic alkoxy, C.sub.3-C.sub.20 alicyclic group, or C.sub.6-C.sub.20 aromatic hydrocarbyl; X is selected from halogen; a=0, 1 or 2; b=0, 1 or 2, and a+b=2.

4. The olefin coordination polymerization catalyst according to claim 1, wherein the magnesium compound includes at least one selected from magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium methoxide chloride, magnesium ethoxide chloride, magnesium propoxide chloride, magnesium butoxide chloride, magnesium phenoxide chloride, magnesium ethoxide, magnesium isopropoxide, magnesium butoxide, magnesium isopropoxide chloride, butyl magnesium chloride, magnesium diethoxide, magnesium dipropoxide, and magnesium dibutoxide.

5. The olefin coordination polymerization catalyst according to claim 4, wherein the magnesium compound is magnesium dichloride, magnesium diethoxide, or magnesium dipropoxide.

6. The olefin coordination polymerization catalyst according to claim 1, wherein the transition metal halide is at least one selected from a compound of formula M(R.sup.1A).sub.4-mX.sub.m, wherein M is Ti, Zr, Hf, Fe, Co, or Ni; X is CI, Br, or F; m is an integer from 1 to 4; R.sup.1A is selected from C.sub.1-C.sub.20 aliphatic hydrocarbyl, C.sub.1-C.sub.20 aliphatic alkoxy, C.sub.1-C.sub.20 cyclopentadienyl group, C.sub.1-C.sub.20 aromatic hydrocarbyl, COR, or COOR, wherein R is an aliphatic hydrocarbyl having C.sub.1-C.sub.10 or an aromatic group having C.sub.1-C.sub.10.

7. The olefin coordination polymerization catalyst according to claim 6, wherein R.sup.1A includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-sulfonylphenyl, formyl, acetyl, or benzoyl.

8. The olefin coordination polymerization catalyst according to claim 6, wherein the transition metal halide is one or a combination of more than one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochloride triethoxide, titanium dichloride diethoxide, titanium trichloride ethoxide, n-butyl titanate, isopropyl titanate, titanium methoxide trichloride, titanium dibutoxide dichloride, titanium tributoxide chloride, titanium tetraphenoxide, titanium monochloride triphenoxide, titanium dichloride diphenoxide, and titanium trichloride monophenoxide.

9. The olefin coordination polymerization catalyst according to claim 8, wherein the transition metal halide is titanium tetrachloride; and a molar ratio of the transition metal halide to the magnesium compound is 8-40:1.

10. The olefin coordination polymerization catalyst according to claim 1, wherein the alcohol having 2 to 15 carbon atoms is at least one selected from ethanol, methanol, propanol, butanol, pentanol, heptanol, isooctanol, n-octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and pentadecanol.

11. The olefin coordination polymerization catalyst according to claim 10, wherein the alcohol having 2 to 15 carbon atoms is at least one of ethanol and isooctanol.

12. A method for polymerization of ethylene, propylene or copolymerization of ethylene or propylene with an -olefin, comprising using the olefin coordination polymerization catalyst according to claim 1; wherein the -olefin is selected from C.sub.3-C.sub.20 olefins.

13. The method according to claim 12, wherein the -olefin is selected from propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1,3-butadiene, isoprene, styrene, methylstyrene, or norbornene.

Description

DETAILED DESCRIPTION

(1) For better understanding of the technical features, objects and advantageous effects of the present invention, the technical solutions of the present invention will now be described in detail below, which are not to be construed as limiting to the scope of the present invention.

(2) The mass percentages of Mg and Ti in the main catalyst were measured by ICP.

(3) The melt index of the polyethylene and polyethylene copolymer was measured under the conditions of a testing load of 5 kg and a temperature of 190 C.

(4) The melting index MFR of the isotactic polypropylene was measured under a testing load of 2.16 kg and a temperature of 230 C.

Example 1

(5) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(6) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 0.25 mL of ethanol, and 6 mL of isooctanol were added, and the mixture was stirred, heated to 120 C., and reacted for 2 h. The temperature was lowered to 60 C., and 1.2 g of a star-shaped organosiloxane compound (Structural Formula 1) was subsequently added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 20 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 70 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 2

(7) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(8) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of n-decane, 0.3 mL of ethanol, and 6.5 mL of isooctanol were added, and the mixture was stirred, heated to 120 C., and reacted for 2 h. The temperature was lowered to 60 C., and 2.5 g of a star-shaped organosiloxane compound (Structural Formula 2) was subsequently added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 10 C., 30 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 110 C., and the reaction was carried out for 3 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 C. for 3 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 3

(9) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(10) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of n-decane, 0.25 mL of ethanol, and 7.5 mL of isooctanol were added, and the mixture was stirred, heated to 110 C., and reacted for 2 h. The temperature was lowered to 50 C., and 2 g of a star-shaped organosiloxane compound (Structural Formula 3) was subsequently added, the temperature was raised to 80 C., and the reaction was carried out for 2 h. The temperature was lowered to 15 C., 30 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 65 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 4

(11) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(12) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 2 mL of ethanol, and 7 mL of isooctanol were added, and the mixture was stirred, heated to 110 C., and reacted for 4 h. The temperature was lowered to 60 C., and 0.85 g of a star-shaped organosiloxane compound (Structural Formula 4) was subsequently added, the temperature was raised to 100 C., and the reaction was carried out for 2 h. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 80 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 5

(13) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(14) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 0.4 mL of ethanol, and 8 mL of isooctanol were added, and the mixture was stirred, heated to 100 C., and reacted for 5 h. The temperature was lowered to 40 C., and 2 g of a star-shaped organosiloxane compound (Structural Formula 5) was subsequently added, and the reaction was carried out for 2 h with the temperature kept at 50 C. The temperature was lowered to 15 C., 35 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 3 h, then the temperature was raised to 120 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 90 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 6

(15) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(16) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 2.5 mL of ethanol, and 2 mL of isooctanol were added, and the mixture was stirred, heated to 120 C., and reacted for 2 h. The temperature was lowered to 60 C., and 3 g of a star-shaped organosiloxane compound (Structural Formula 6) and 6 mL of tetraethoxysilane were subsequently added, and the reaction was carried out for 3 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 40 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 70 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 80 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 7

(17) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(18) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of n-decane, and 0.25 mL of ethanol were added, and the mixture was stirred, heated to 120 C., and reacted for 4 h. The temperature was lowered to 50 C., and 2 g of a star-shaped organosiloxane compound (Structural Formula 7) and 0.4 mL of ethanol were added, and the reaction was carried out for 4 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 35 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 90 C., and the reaction was carried out for 4 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with toluene (30 ml each time) and four times with hexane (30 ml each time), and dried under vacuum at 60 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 8

(19) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(20) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of dodecane, 0.4 mL of ethanol, and 6 mL of decanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 70 C., and 2 g of a star-shaped organosiloxane compound (Structural Formula 8) was subsequently added, and the reaction was carried out for 3 h with the temperature kept at 70 C. The temperature was lowered to 10 C., 30 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 3 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 9

(21) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(22) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of toluene, and 0.2 mL of propanol were added, and the mixture was stirred, heated to 120 C., and reacted for 5 h. The temperature was lowered to 50 C., and 1.5 g of a star-shaped organosiloxane compound (Structural Formula 9) was added, and the reaction was carried out for 2 h with the temperature kept at 50 C. The temperature was lowered to 0 C., 25 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 120 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 80 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 10

(23) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(24) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of n-octane, 2.5 mL of butanol, and 7 mL of isooctanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 60 C., and 2 g of a star-shaped organosiloxane compound (Structural Formula 10) was added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 40 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 90 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 11

(25) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(26) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 25 mL of n-decane, and 5 mL of ethanol were added, and the mixture was stirred, heated to 120 C., and reacted for 2 h. The temperature was lowered to 50 C., and 1.5 g of a star-shaped organosiloxane compound (Structural Formula 11) was added, and the reaction was carried out for 2 h with the temperature kept at 50 C. The temperature was lowered to 25 C., 25 mL of titanium tetrachloride at 10 C. was then added dropwise, the reaction was carried out for 1 h at 0 C., then the temperature was raised to 110 C. in 2 h, and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 12

(27) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(28) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 40 mL of n-decane, and 2.5 mL of ethanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 60 C., and 1.5 g of an electron-donating star-shaped organosiloxane compound (Structural Formula 12) and 8 mL of tetraethoxysilane were added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 35 mL of titanium tetrachloride at 15 C. was then added dropwise, the reaction was carried out for 1 h at 15 C., then the temperature was raised to 120 C. in 3 h, and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 13

(29) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(30) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, and 3 mL of isooctanol were added, and the mixture was stirred, heated to 110 C., and reacted for 3 h. The temperature was lowered to 50 C., and 1.5 g of an electron-donating star-shaped organosiloxane compound (Structural Formula 13) was added, and the reaction was carried out for 2 h at 50 C. The temperature was lowered to 0 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 110 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 50 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 14

(31) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(32) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 10 mL of toluene, 2 mL of ethanol, and 6.5 mL of isooctanol were added, and the mixture was stirred, heated to 100 C., and reacted for 4 h. The temperature was lowered to 40 C., 2 g of an electron-donating star-shaped organosiloxane compound (Structural Formula 14) and 0.15 g of silica gel were added, and the temperature was raised to 70 C. and the reaction was carried out for 2 h. The temperature was lowered to 15 C., 15 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 95 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 15

(33) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(34) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of n-decane, 6.5 mL of isooctanol, and 0.25 mL of ethanol were added, and the mixture was stirred, heated to 120 C., and reacted for 2 h. The temperature was lowered to 50 C., 3 g of an electron-donating star-shaped organic heteroether compound (Structural Formula 15) and 15 mL of succinate were added, and the reaction was carried out for 3 h with the temperature kept at 50 C. The temperature was lowered to 15 C., 20 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 90 C., and the reaction was carried out for 2 h. The reaction mixture was dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 16

(35) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(36) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 10 mL of toluene, 2 mL of ethanol, and 6.5 mL of isooctanol were added, and the mixture was stirred, heated to 100 C., and reacted for 4 h. The temperature was lowered to 40 C., 6 g of an electron-donating star-shaped organic heteroether compound (Structural Formula 16) was added, and the temperature was raised to 90 C. and the reaction was carried out for 2 h. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 120 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 17

(37) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(38) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 20 mL of toluene, 2 mL of ethanol, and 7 mL of isooctanol were added, and the mixture was stirred, heated to 100 C., and reacted for 4 h. The temperature was lowered to 60 C., 2.5 g of an electron-donating star-shaped organic heteroether compound (Structural Formula 17) and 0.05 mL of tetraethoxysilane were added, and the temperature was raised to 70 C. and the reaction was carried out for 2 h. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 110 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 18

(39) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(40) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride and 30 mL of n-hexane were added, and the mixture was stirred, heated to 80 C., and reacted for 4 h. The temperature was lowered to 60 C., 5.5 g of an electron-donating star-shaped organic heteroether compound (Structural Formula 18) was added, and the temperature was raised to 80 C. and the reaction was carried out for 2 h. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Example 19

(41) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(42) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 30 mL of cyclohexane, 6 mL of isooctanol, and 0.25 mL of ethanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 60 C., 4.5 g of an electron-donating star-shaped organic heteroether compound (Structural Formula 19) was added, and the temperature was raised to 80 C. and the reaction was carried out for 4 h. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 110 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with cyclohexane (30 ml each time) and twice with hexane (30 ml each time), and dried under vacuum at 80 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

Comparative Example 1

(43) This comparative example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(44) In a reactor sufficiently purged with nitrogen, 1 g of diethoxymagnesium, 20 mL of decane, 6 mL of isooctanol, and 0.25 mL of ethanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 60 C., 3 mL of tetraethoxysilane was added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 80 C. for 2 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity and uniform particle size distribution, although the main catalyst particles tended to adhere to the walls of the container.

Comparative Example 2

(45) This comparative example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(46) In a reactor sufficiently purged with nitrogen, 1 g of diethoxymagnesium, 20 mL of decane, 6 mL of isooctanol, and 0.25 mL of ethanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 60 C., 3 mL of tributyl phosphate and 3 mL of tetraethoxysilane were added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst, although the main catalyst particles tended to adhere to the walls of the container.

Comparative Example 3

(47) This comparative example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(48) In a reactor sufficiently purged with nitrogen, 1 g of diethoxymagnesium, 20 mL of decane, 6 mL of isooctanol, and 0.25 mL of ethanol were added, and the mixture was stirred, heated to 100 C., and reacted for 2 h. The temperature was lowered to 60 C., 3 mL of tributyl phosphate was added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 15 C., 25 mL of titanium tetrachloride was then added dropwise, the reaction was carried out for 1 h, then the temperature was raised to 100 C., and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed twice with hexane (30 ml each time), and dried under vacuum at 60 C. for 2 h to obtain a powdery solid main catalyst, but the main catalyst particles tended to adhere to the walls of the container.

Application Example 1

(49) Ethylene polymerization: after a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 1 mg of the main catalyst, 1000 mL of dehydrated hexane, and 1.5 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 75 C. before hydrogen was charged to 0.28 MPa and ethylene was further charged to 0.73 MPa. The reaction was carried out under constant pressure at a constant temperature for 2 h. The result of olefin polymerization is shown in Table 1.

Application Example 2

(50) Ethylene copolymerization: after a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 10 mg of the main catalyst, 1000 mL of dehydrated hexane, and 1.5 mL of AlEt.sub.3 solution (2 mmol/mL) were sequentially added to the autoclave, and 30 mL of 1-hexene was added, and the temperature was raised to 75 C. Then 0.28 MPa of hydrogen was charged, and ethylene was charged to 0.73 MPa. The reaction was carried out under constant pressure at a constant temperature for 2 h. The result of olefin polymerization is shown in Table 1.

Application Example 3

(51) Propylene polymerization: after a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 10 mg of the main catalyst, 1000 mL of dehydrated hexane, and 1.5 mL of AlEt.sub.3 solution (2 mmol/mL) were sequentially added to the autoclave, 4 mL of electron-donating triethoxycyclopentyloxysilane (a 0.18 M solution in hexane), and the temperature was raised to 80 C. Then 0.1 MPa of hydrogen was charged, and propylene was charged to 3 MPa. The reaction was carried out under constant pressure at a constant temperature for 2 h. The result of olefin polymerization is shown in Table 1.

Example 20

(52) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(53) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 2.5 mL of ethanol, and 6.5 mL of isooctanol were added, and the mixture was stirred, heated to 120 C., and reacted for 3 h. The temperature was lowered to 60 C., and 2 g of an electron-donating star-shaped organosiloxane compound (Structural Formula 3) and 0.2 mL of tetraethoxysilane were added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 5 C., 35 mL of titanium tetrachloride was added dropwise, the reaction was carried out for 1 h; then the temperature was raised to 110 C. in 4 h, and the reaction was carried out for 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

(54) Ethylene Polymerization

(55) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 5 mg of the above-mentioned main catalyst of the present example, 1000 mL of dehydrated hexane, 0.6 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.1 MPa and ethylene was further charged to 0.8 MPa. The reaction was carried out under constant pressure at a constant temperature for 1 h.

(56) 375.2 g of polyethylene was obtained, with a bulk density BD=0.34 and a melt index MFR=0.1 g/10 min.

(57) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 10 mg of the main catalyst, 1000 mL of dehydrated hexane, 0.6 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.28 MPa and ethylene was further charged to 0.73 MPa. The reaction was carried out under constant pressure at a constant temperature for 2 h.

(58) 355.5 g of polyethylene was obtained, with a bulk density BD=0.34 and a melt index MFR=1.6 g/10 min.

(59) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 25 mg of the above-mentioned main catalyst of the present example, 1000 mL of dehydrated hexane, 3.0 mL of a AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.73 MPa and ethylene was further charged to 1.0 MPa. The reaction was carried out under constant pressure at a constant temperature for 1 h. 263.6 g of polyethylene was obtained, with a bulk density BD=0.35 and a melt index MFR=480 g/10 min.

Example 21

(60) This example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(61) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 2.5 mL of ethanol, and 6.5 mL of isooctanol were added, and the mixture was stirred, heated to 120 C., and reacted for 3 h. The temperature was lowered to 60 C., and 1.2 g of an electron-donating star-shaped organosiloxane compound (1) and 0.2 mL of tetraethoxysilane were added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 25 C., 25 mL of titanium tetrachloride at 15 C. was added dropwise, the reaction was carried out for 1 h at 0 C., then the temperature was raised to 110 C. in 4 h, and the reaction was carried out for another 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity, non-stickiness to the walls of the container, and uniform particle size distribution.

(62) Ethylene Polymerization

(63) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 5 mg of the above-mentioned main catalyst of the present example, 1000 mL of dehydrated hexane, 0.6 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.1 MPa and ethylene was further charged to 0.6 MPa. The reaction was carried out under constant pressure at a constant temperature for 1 h.

(64) 285.3 g of polyethylene was obtained, with a bulk density BD=0.33 and a melt index MFR=0.18 g/10 min.

(65) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 10 mg of the above-mentioned main catalyst of the present example, 1000 mL of dehydrated hexane, 0.6 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.28 MPa and ethylene was further charged to 0.73 MPa. The reaction was carried out under constant pressure at a constant temperature for 2 h.

(66) 361.3 g of polyethylene was obtained, with a bulk density BD=0.33 and a melt index MFR=1.7 g/10 min.

(67) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 25 mg of the main catalyst, 1000 mL of dehydrated hexane, 3.0 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.73 MPa and ethylene was further charged to 1.0 MPa. The reaction was carried out under constant pressure at a constant temperature for 1 h.

(68) 258.1 g of polyethylene was obtained, with a bulk density BD=0.34 and a melt index MFR=490 g/10 min.

Comparative Example 4

(69) This comparative example provides a method for preparing a main catalyst of an olefin coordination polymerization catalyst, which specifically comprises the following steps:

(70) In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 mL of n-decane, 6.5 mL of isooctanol, and 2.5 mL of ethanol were added, and the mixture was stirred, heated to 120 C., and reacted for 3 h. The temperature was lowered to 60 C., and 0.2 mL of tetraethoxysilane were added, and the reaction was carried out for 2 h with the temperature kept at 60 C. The temperature was lowered to 25 C., 25 mL of titanium tetrachloride at 15 C. was added dropwise, the reaction was carried out for 1 h at 0 C.; then the temperature was raised to 110 C. in 4 h, and the reaction was carried out for another 2 h. Stirring was stopped, and the reaction mixture was allowed to stand, separated in layers, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 C. for 4 h to obtain a powdery solid main catalyst in a spherical shape with good fluidity and uniform particle size distribution, although the main catalyst particles tended to adhere to the walls of the container.

(71) Ethylene Polymerization

(72) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 10 mg of the above-mentioned main catalyst, 1000 mL of dehydrated hexane, 0.6 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.1 MPa and ethylene was further charged to 0.8 MPa. The reaction was carried out under constant pressure at a constant temperature for 1 h.

(73) 235.3 g of polyethylene was obtained, with a bulk density BD=0.30 and a melt index MFR=0.3 g/10 min.

(74) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 10 mg of the main catalyst, 1000 mL of dehydrated hexane, 0.6 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.28 MPa and ethylene was further charged to 0.73 MPa. The reaction was carried out under constant pressure at a constant temperature for 2 h.

(75) 188.3 g of polyethylene was obtained, with a bulk density BD=0.28 and a melt index MFR=3.1 g/10 min.

(76) After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 50 mg of the main catalyst, 1000 mL of dehydrated hexane, 3.0 mL of an AlEt.sub.3 solution (2 mmol/mL) as a cocatalyst were sequentially added to the autoclave, and the temperature was raised to 70 C. before hydrogen was charged to 0.73 MPa and ethylene was further charged to 1.0 MPa. The reaction was carried out under constant pressure at a constant temperature for 1 h.

(77) 172.1 g of polyethylene was obtained, with a bulk density BD=0.26 and a melt index MFR=126 g/10 min.

(78) TABLE-US-00001 TABLE 1 Catalytic Catalytic Titanium Catalytic efficiency efficiency content in efficiency in in Appli- of Appli- the main Application cation cation Bulk catalyst Example 1 Example 2 Example 3 density Examples (wt %) (kg/g cat) (kg/g cat) (kg/g cat) (g/cm.sup.3) 1 5.0 28 30 0.34 2 4.8 29 31 0.33 3 5.1 27 26 0.34 4 5.2 28 28 0.34 5 5.3 27 27 0.35 6 5.2 29 30 0.33 7 4.8 27 29 0.32 8 4.8 27 24 0.31 9 5.1 24 28 0.32 10 4.7 25 26 0.33 11 4.8 27 28 0.33 12 4.9 25 25 0.32 13 5.3 24 24 0.33 14 5.2 24 22 0.31 15 3.8 33 0.47 16 5.2 24 25 0.32 17 5.1 25 26 0.36 18 5.0 27 28 0.40 19 4.9 25 26 0.35 Comparative 5.0 19 20 0.28 Example 1 Comparative 5.1 18 21 0.26 Example 2 Comparative 5.1 20 20 0.29 Example 3

(79) The above examples demonstrate that the olefin coordination polymerization catalyst of the present invention has a high catalytic activity and a simple preparation process.