Catalyst component for olefin polymerization, preparation method therefor and catalyst thereof

Abstract

A catalyst component (A) for olefin polymerization is prepared by contacting a solid component (a) containing magnesium, titanium, halogen and an internal electron donor compound with an organosilicon compound (b), wherein the organosilicon compound (b) is one or more selected from a SiH functional group containing chainlike polysiloxane (b1) represented by formula (I.sub.x), a cyclic polysiloxane (b2) represented by formula (I.sub.y) and a SiH functional group containing organosilicon compound (b3) represented by formula (I.sub.z). In addition, a process for preparing the catalyst component and the corresponding catalyst is described. The catalyst component and its catalyst have high catalytic activity, good hydrogen response, and good stereospecificity, the catalyst can release its activity more evenly, and the obtained polymer has significantly increased bulk density. The definitions of R.sup.1 to R.sup.10, n and z in the formulae (I.sub.x), (l.sub.y) and (I.sub.z) are as described in the specification. ##STR00001##

Claims

1. A catalyst component for olefin polymerization, wherein the catalyst component is prepared by contacting a solid component containing magnesium, titanium, halogen and an internal electron donor compound with an organosilicon compound, wherein the organosilicon compound is one or more selected from the group consisting of a SiH functional group containing chainlike polysiloxane represented by formula (I.sub.x), and a SiH functional group containing organosilicon compound represented by formula (I.sub.z): ##STR00005## in the formula (I.sub.x), R.sup.1-R.sup.7, which are identical or different, independently of each other represent one selected from the group consisting of a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an alkaryl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; the degree of polymerization n is an integer of 2 to 100;
HSiR.sup.9.sub.zR.sup.10.sub.3-z(I.sub.z) in the formula (I.sub.z), R.sup.9 and R.sup.10, which are identical or different, independently of each other represent one selected from the group consisting of a hydrogen atom, a halogen atom, a linear or branched saturated alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an alkaryl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R.sup.9 and R.sup.10 are not simultaneously hydrogen; z is an integer of 0 to 3, wherein the solid component is prepared by suspending the magnesium compound in an inert diluent to form a suspension and then bringing the suspension into contact with the titanium compound and the internal electron donor, and wherein the catalyst component a content of titanium atoms is 1.0-8.0 wt %, a content of magnesium atoms is 10-70 wt %, a content of a halogen atoms is 20-86 wt %, a content of silicon atoms is 0.01-0.5 wt %, and a content of the internal electron donor compound is 2-30 wt %.

2. The catalyst component according to claim 1, wherein an alkoxy magnesium compound represented by formula (II) or an alcohol adduct of the alkoxy magnesium compound represented by formula (II) is used as the magnesium compound for preparing the solid component,
Mg(OR.sup.11).sub.2-y(OR.sup.12).sub.y(II) in the formula (II), R.sup.11 and R.sup.12, which are identical or different, independently of each other represent a linear or branched alkyl group having 1 to 8 carbon atoms, and 0y2.

3. The catalyst component according to claim 1, wherein the titanium compound used for preparing the solid component is a compound represented by formula (III),
TiX.sub.m(OR).sub.4-m(III) in the formula (III), X is a halogen atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is an integer of 0 to 4; wherein the halogen is chlorine, bromine or iodine.

4. The catalyst component according to claim 3, wherein the titanium compound is titanium tetrachloride.

5. The catalyst component according to claim 1, wherein the internal electron donor compound used for preparing the solid component is one or more compound represented by formula (IV), ##STR00006## in the formula (IV), R.sup.13 and R.sup.14, which are identical or different, independently of each other represent one selected from the group consisting of a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an alkaryl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are all hydrogen; or three of them are hydrogen and the other one is a group selected from the group consisting of a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched alkoxy group having 1 to 4 carbon atoms.

6. The catalyst component according to claim 5, wherein the internal electron donor is at least one selected from the grow consisting of diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, and diisooctyl phthalate.

7. The catalyst component according to claim 1, wherein the organosilicon compound is a SiH functional group containing organosilicon compound represented by the formula (I.sub.z), which is at least one selected from the group consisting of triethylsilane, tripropylsilane, tributyl silane, tripentyl silane, trihexyl silane, triisopropylsilyl, triphenyl silane, diphenyl silane, dipropyl silane, dibutyl silane, dipentyl silane, dihexyl silane, diisopropyl silane, diisobutyl silane, diisopentyl silane, and diisohexyl silane.

8. The catalyst component according to claim 1, wherein the organosilicon compound is a chainlike polysiloxane represented by the formula (I.sub.x), wherein R.sup.1 is a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group or an aryl group, and R.sup.2-R.sup.7 are methyl.

9. The catalyst component according to claim 8, wherein the chainlike polysiloxane represented by the formula (I.sub.x) is at least one selected from the group consisting of 1,1,1,3,5,7,7,7-octamethyltetrasiloxane (n=2), polymethylhydrosiloxane, polyethylhydrosiloxane, polyphenylhydrosiloxane, and polycyclohexylhydrosiloxane.

10. The catalyst component according to claim 1, wherein in the catalyst component, the content of titanium atoms is 1.6-4.0 wt %; the content of magnesium atoms is 15-40 wt %; the content of halogen atoms is 36-80%; the content of silicon atoms is 0.02-0.5 wt %; the content of the internal electron donor compound is 3-20 wt %.

11. A process for preparing the catalyst component according to claim 1, the process comprising contacting the organosilicon compound with the solid component as has been already prepared into reaction.

12. A process for preparing the catalyst component according to claim 1, wherein the organosilicon compound is added to effect the reaction during the preparation of the solid component which, in time sequence, comprises the following three steps: forming mother liquor, titanium treatment and washing; wherein the step of forming mother liquor comprises suspending a magnesium compound in an inert diluent to form a suspension, and then bringing the suspension into contact with a titanium compound and an internal electron donor to obtain a solid dispersion system, which is called as a mother liquor; the titanium treatment step comprises filtering the mother liquor, and suspending the resulting solid substance in a titanium tetrachloride-containing solution to effect treatment; and the washing step comprises filtering and washing the solid substance obtained in the preceding step.

13. The process according to claim 12, wherein the organosilicon compound is added after the step of forming the mother liquor and before the titanium treatment step during the preparation of the solid component.

14. The process according to claim 12, wherein the organosilicon compound is added in the titanium treatment step during the preparation of the solid component.

15. The process according to claim 12, wherein the organosilicon compound is added in the washing step after the titanium treatment step during the preparation of the solid component.

16. A catalyst for olefin polymerization, which comprises the catalyst component according to claim 1, and further comprises an organoaluminum compound as cocatalyst, and optionally an external electron donor compound.

17. The catalyst according to claim 16, wherein the organoaluminum compound is at least one selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride and ethylaluminum dichloride.

18. The catalyst according to claim 16, wherein the external electron donor compound is an organosilicon compound represented by formula (VI):
R.sup.1.sub.mR.sup.2.sub.nSi(OR.sup.3).sub.4-m-n(VI) wherein, R.sup.1 and R.sup.2, which are identical or different, independently of each other are selected from the group consisting of a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and a haloalkyl group having 1 to 20 carbon atoms; R.sup.3 is one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and a haloalkyl group having 1 to 20 carbon atoms; m and n are respectively an integer of 0 to 3, and m+n<4.

19. The catalyst according to claim 16, wherein the external electron donor compound is at least one selected from the group consisting of dicyclopentyl dimethoxysilane, diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, cyclohexylmethyl dimethoxysilane, diphenyl dimethoxysilane, methyltert-butyl dimethoxysilane, and tetraethoxysilane.

20. A process for homopolymerization and copolymerization of olefins, the process comprising utilizing the catalyst component according to claim 1, wherein at least one of the olefins is an olefin represented by formula CH.sub.2CHR, wherein R is hydrogen or an alkyl group having 1 to 6 carbon atoms.

21. The process according to claim 20, wherein the olefin is ethylene, propylene or 1-n-butene.

22. A process for homopolymerization and copolymerization of olefins, the process comprising utilizing the catalyst according to claim 16, wherein at least one of the olefins is an olefin represented by formula CH.sub.2CHR, wherein R is hydrogen or an alkyl group having 1 to 6 carbon atoms.

23. The process according to claim 22, wherein the olefin is ethylene, propylene or 1-n-butene.

Description

MODE OF CARRYING OUT THE PRESENT INVENTION

(1) The present invention is further described in detail by referring to the following examples. The following examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to these examples. Any change or variation that can be easily accomplished by a person skilled in the art within the technical scope disclosed in the present disclosure is embraced within the protection scope of the present invention. The scope of the present invention is proposed in the claims.

(2) Unless specified otherwise, the organosilicon compounds used in the following examples were all purchased from ACROS or Sigma-Aldrich Co.; anhydrous MgCl.sub.2 was purchased from Qinghai Beichen Science and Technology Co., Ltd.; TiCl.sub.4 was purchased from Xingtai Non-Ferrous Smelter; the organosilicon compound as external electron donor and the organoaluminum compound as cocatalyst both were purchased from Nanjing Tonglian Chemical Industry Co., Ltd.

(3) In the following examples, the contents of titanium atoms in the solid component (a) and the catalyst component (A) for olefin polymerization were measured by using a 721 spectrophotometer purchased from UNCOMMON (Tianjin) Science and Technology Development Co., Ltd.; the melt index of polymer was measured by using a XRZ-00 melt flow rate tester purchased from Changchun Shinco Experimental Instruments and Equipments Co., Ltd., in accordance with the method specified in GB/T3682-2000.

(4) In the following examples, the content of silicon atoms was measured according to the following method:

(5) At first, the relative contents of Si and Ti atoms in the catalyst were measured by using an Axios-Advanced X-ray fluorescence spectrometer purchased from Dutch PANalytical Co., and then the content of Si atoms was calculated in virtue of the above-mentioned content of Ti atoms that was measured by the spectrometer according to the following formula:
the content of Si atoms=(the content of Ti atomsthe relative content of Si atoms)the relative content of Ti atoms.

(6) In the following examples, the isotacticity of polymer was measured according to the following method: 2 g of dried polymer sample was extracted by using boiling heptane in an extractor for 6 hours, the residue was dried till constant weight, and the isotacticity was calculated according to the following formula:
Isotacticity (%)=mass of the polymer after extraction/2100.

(7) Bulk density of polymer: polymer powders dropped from a hopper to a 100 mL cylindrical vessel, the mass in grams of the polymer in the vessel was weighed, and bulk density of the polymer was calculated according to the following formula:
Bulk density (BD)=m/100 g/cm.sup.3.

PREPARATORY EXAMPLE

(8) Preparation of Alkoxy Magnesium:

(9) In a 1 L reactor equipped with a stirrer, a reflux condenser, a thermometer and a constant pressure addition funnel, which had been sufficiently purged with nitrogen gas, 550 mL of ethanol, 10 mL of isopropyl alcohol, and 0.68 g of iodine were added and dissolved. The reaction system was heated with stirring until reaching its reflux temperature. Then, 32 g of magnesium powder was added successively. The reaction was carried out until no discharge of hydrogen gas, thereafter the reaction product was washed, filtered and dried to give 147 g of alkoxy magnesium having a bulk density of 0.25 g/cm.sup.3, and an average particle diameter (D50) of 47.0 m.

Example 1

(10) Preparation of Solid Component (a1):

(11) 10 g of the alkoxy magnesium support prepared in Preparatory Example, 50 mL of toluene and 2.5 mL of di-n-butyl phthalate were formulated into a suspension. In a 300 mL reaction kettle which had been repetitively purged with highly pure nitrogen gas, 40 mL of toluene and 60 mL of titanium tetrachloride were added, and then the formulated suspension was added. The reaction kettle was heated up to 80 C., kept at this temperature for 1 hour, then continuously heated up to 115 C., and kept at this temperature for 2 hours. Thereafter, the liquid (mother liquor) was filtered thoroughly. Then, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added to the resulting solid, and heated up to 110 C. with stirring to carry out treatment for 1 hour (titanium treatment). The treatment was repeated for three times, and thereafter the liquid was filtered off and the resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times. After filtering off the liquid, the resulting solid was dried to give a solid component (a1) of the present invention. The resulting solid component (a1) had a content of titanium of 2.4 wt %.

(12) Preparation of Catalyst Component (A1) for Olefin Polymerization:

(13) In a 300 mL reaction kettle, 10 g of the solid component (a1) and 80 mL of n-heptane were added, and the mixture was cooled down to 10 C., to which was then added 3 mL of polymethylhydrosiloxane (n35) with stirring to form a suspension. The suspension was heated up to 70 C., kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-heptane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A1) for olefin polymerization. The catalyst component (A1) for olefin polymerization had a content of titanium atoms of 2.1 wt %, and a content of silicon atoms of 0.060 wt %.

(14) Preparation of Polyolefin:

(15) In a 5 L autoclave which had been sufficiently purged with gas phase propylene, 5 mL of a solution of triethylaluminum in hexane (concentration of triethylaluminum: 0.5 mol/L), 1 mL of a solution of cyclohexylmethyl dimethoxysilane (CHMMS) in hexane (concentration of CHMMS: 0.1 mol/L), 10 mL of anhydrous hexane and about 6-10 mg of the catalyst component (A1) for olefin polymerization as above prepared were added at room temperature. The autoclave was closed, to which 0.9 standard liters (NL) of hydrogen gas and 2 L of liquid propylene were introduced. With stirring, the temperature was raised up to 70 C. within 15 minutes. After polymerization at 70 C. for 1-3 hours, the stirring was stopped, the remnant propylene monomer was removed, and the resulting product was collected to give a polymer P.

(16) The results as to the polymerization activity of the catalyst component (A1) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1. The polymerization activity of the catalyst was calculated according to the following formula:
Polymerization activity=mass of the polymer P (kg)/mass (g) of the catalyst component (A1) for olefin polymerization.

Comparative Example 1

(17) The solid component (a1) as prepared in Example 1 was used in place of the catalyst component (A1) for olefin polymerization to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the solid component (a1), the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 2

(18) Preparation of Catalyst Component (A2) for Olefin Polymerization:

(19) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 80 mL of n-hexane were added, and the mixture was cooled down to 0 C., to which was then added 3 mL of polymethylhydrosiloxane (n6) with stirring to form a suspension. The suspension was heated up to 60 C., kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A2) for olefin polymerization. The catalyst component (A2) for olefin polymerization had a content of titanium atoms of 2.1 wt %, and a content of silicon atoms of 0.090 wt %.

(20) Preparation of Polyolefin:

(21) A2 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A2) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 3

(22) Preparation of catalyst component (A3) for olefin polymerization:

(23) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 100 mL of n-hexane were added with stirring to form a suspension. The suspension was heated up to 60 C., to which then 0.5 mL of polymethylhydrosiloxane (n35) was added, and kept at this temperature for 3 hours. Then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A3) for olefin polymerization. The catalyst component (A3) for olefin polymerization had a content of titanium atoms of 2.0 wt %, and a content of silicon atoms of 0.042 wt %.

(24) Preparation of Polyolefin:

(25) A3 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A3) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 4

(26) Preparation of Catalyst Component (A4) for Olefin Polymerization:

(27) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 100 mL of n-heptane were added, and the mixture was cooled down to 0 C., to which was then added 3 mL of tetramethylcyclotetrasiloxane with stirring to form a suspension. The suspension was heated up to 70 C., kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-heptane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A4) for olefin polymerization. The catalyst component (A4) for olefin polymerization had a content of titanium atoms of 2.1 wt %, and a content of silicon atoms of 0.080 wt %.

(28) Preparation of Polyolefin:

(29) A4 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A4) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 5

(30) Preparation of Catalyst Component (A5) for Olefin Polymerization:

(31) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 100 mL of n-hexane were added with stirring to form a suspension. The suspension was heated up to 60 C., to which 3 mL of tetraethylcyclotetrasiloxane was added, and kept at this temperature for 2 hours. Then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A5) for olefin polymerization. The catalyst component (A5) for olefin polymerization had a content of titanium atoms of 2.1 wt %, and a content of silicon atoms of 0.075 wt %.

(32) Preparation of Polyolefin:

(33) A5 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A5) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 6

(34) Preparation of Catalyst Component (A6) for Olefin Polymerization:

(35) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 70 mL of n-hexane were added, and the mixture was cooled down to 0 C., to which was then added 3 mL of pentamethylcyclopentasiloxane with stirring to form a suspension. The suspension was heated up to 60 C., kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A6) for olefin polymerization. The catalyst component (A6) for olefin polymerization had a content of titanium atoms of 2.0 wt %, and a content of silicon atoms of 0.060 wt %.

(36) Preparation of Polyolefin:

(37) A6 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A6) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 7

(38) Preparation of Catalyst Component (A7) for Olefin Polymerization:

(39) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 100 mL of n-hexane were added with stirring to form a suspension. The suspension was heated up to 60 C., to which then 0.5 mL of tetramethylcyclotetrasiloxane was added, and kept at this temperature for 3 hours. Then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A7) for olefin polymerization. The catalyst component (A7) for olefin polymerization had a content of titanium atoms of 2.2 wt %, and a content of silicon atoms of 0.032 wt %.

(40) Preparation of Polyolefin:

(41) A7 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A7) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 8

(42) Preparation of Catalyst Component (A8) for Olefin Polymerization:

(43) 10 g of diethoxy magnesium support prepared in Preparatory Example, 50 mL of toluene and 2.5 mL of di-n-butyl phthalate were formulated into a suspension. In a 300 mL reaction kettle which had been repetitively purged with highly pure nitrogen gas, 40 mL of toluene and 60 mL of titanium tetrachloride were added, and then the formulated suspension was added. The reaction kettle was heated up to 80 C., kept at this temperature for 1 hour, then continuously heated up to 115 C., and kept at this temperature for 2 hours. Thereafter, the liquid (mother liquor) was filtered thoroughly. Then, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added to the resulting solid, and heated up to 110 C. to carry out treatment with stirring for 1 hour, and then the liquid was filtered off. The treatment was repeated for two times. Thereafter, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added, and heated up to 110 C., to which 2.0 mL of polymethylhydrosiloxane (n35) was added with stirring. The mixture was kept at this temperature to carry out treatment with stirring for 1 hour, and then the liquid was filtered off. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, and after filtering off the liquid, the resulting solid was dried to give a catalyst component (A8) for olefin polymerization. The catalyst component (A8) for olefin polymerization had a content of titanium atoms of 2.9 wt %, and a content of silicon atoms of 0.125 wt %.

(44) Preparation of Polyolefin:

(45) A8 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A8) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 9

(46) Preparation of Catalyst Component (A9) for Olefin Polymerization:

(47) 10 g of diethoxy magnesium support prepared in Preparatory Example, 50 mL of toluene and 2.5 mL of di-n-butyl phthalate were formulated into a suspension. In a 300 mL reaction kettle which had been repetitively purged with highly pure nitrogen gas, 30 mL of toluene and 120 mL of titanium tetrachloride were added. Then the formulated suspension was added. The reaction kettle was heated up to 80 C., kept at this temperature for 1 hour, then continuously heated up to 115 C., and kept at this temperature for 2 hours. Thereafter, the liquid (mother liquor) was filtered thoroughly. Then, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added to the resulting solid, and heated up to 110 C. to carry out treatment with stirring for 1 hour, and then the liquid was filtered off. The treatment was repeated for three times. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 2 times. Then, 120 ml of hexane was added, and heated up to 60 C., to which 3 mL of polymethylhydrosiloxane (n35) was added with stirring, and kept at this temperature for 2 hours, and then the liquid was filtered off. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 2 times, and after filtering off the liquid, the resulting solid was dried to give a catalyst component (A9) for olefin polymerization. The catalyst component (A9) for olefin polymerization had a content of titanium atoms of 2.0 wt %, and a content of silicon atoms of 0.081 wt %.

(48) Preparation of Polyolefin:

(49) A9 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component (A9) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Comparative Example 2

(50) Preparation of Catalyst Component D1 for Olefin Polymerization:

(51) In a 300 mL reaction kettle, 10 g of the solid component (a1)) prepared in Example 1 and 80 mL of n-heptane were added, and the mixture was cooled down to 10 C., to which was added 3 mL of polydimethylsiloxane (viscosity: 100 centistokes, Qingdao Xingye Silicone New Material Co., Ltd.) with stirring to form a suspension. The suspension was heated up to 70 C., kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-heptane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component D1 for olefin polymerization. The catalyst component D1 for olefin polymerization had a content of titanium atoms of 2.3 wt %.

(52) Preparation of Polyolefin:

(53) D1 was used in place of A1 to carry out the polymerization according to the preparation process of polyolefin described in Example 1. The results as to the polymerization activity of the catalyst component D1 for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 1.

Example 10

(54) Liquid Phase Bulk Polymerization of 1-Butene:

(55) In a 2 L autoclave which had been sufficiently purged with 1-butene, 2 mL of a solution of triethylaluminum in hexane (concentration of triethylaluminum: 0.5 mmol/mL), 0.5 mL of a solution of diisopropyl dimethoxysilane in hexane (concentration: 0.1 mmol/mL), 10 mL of anhydrous hexane and 10 mg of the catalyst component (A1) for olefin polymerization prepared in Example 1 were added at room temperature. The autoclave was closed, to which 2 standard liters (NL) of hydrogen gas and 350 g of liquid 1-butene were introduced. With stirring, the temperature was raised up to 60 C. within 15 minutes. After polymerization at 60 C. for 1-3 hours, the stirring was stopped, the remnant 1-butene monomer was removed, and the resulting product was collected as a polymer.

(56) The results as to the 1-butene polymerization activity of the catalyst component (A1) for olefin polymerization, and the melt index (Ml) of the polymer were shown in Table 1.

Comparative Example 3

(57) The solid component (a1) prepared in Example 1 was used in place of the catalyst component (A1) for olefin polymerization to carry out the polymerization according to the preparation process of polyolefin described in Example 10. The results as to the 1-butene polymerization activity of the solid component (a1), and the melt index (Ml) of the polymer were shown in Table 1.

(58) TABLE-US-00001 TABLE 1 Polymerization activity (Kg .Math. PP/g .Math. Cat) MI II BD 1 hour 2 hours 3 hours (g/10 min) (%) g/cm.sup.3 Example 1: 44 85 117 6.2 98.3 0.44 A1 Example 2: 45 87 115 5.7 98.5 0.44 A2 Example 3: 43 77 105 5.7 98.6 0.44 A3 Example 4: 41 81 107 6.1 98.3 0.44 A4 Example 5: 43 78 110 5.8 98.8 0.45 A5 Example 6: 42 75 103 5.4 98.3 0.44 A6 Example 7: 42 74 105 5.7 98.6 0.44 A7 Example 8: 48 91 118 8.0 97.6 0.43 A8 Example 9: 50 88 114 5.2 98.5 0.44 A9 Comparative 45 69 87 5.4 98.6 0.42 Example 1: a1 Comparative 45 68 85 5.2 98.7 0.42 Example 2: D1 Example 10: 14 25 32 1.1 A1 Comparative 15 22 29 0.9 Example 3: a1 Notes: 1, 2 and 3 hours in the table refer to that the olefin polymerization reaction, in three experiments, had been carried out for 1 hour, 2 hours and 3 hours respectively. MI, II (isotacticity) and BD values in the table were all the measured results of polymer samples taken from one hour polymerization in various examples.

(59) As can be seen from the data in Table 1, the catalyst for olefin polymerization, which was prepared by using the catalyst component for olefin polymerization that had been treated by contacting with the SiH containing organosilicon compound (b1) or (b2), could release activity more steadily and evenly, have better hydrogen response and significantly improved total activity, and could result in polymer having increased bulk density, as compared with the catalyst for olefin polymerization which was prepared by using an untreated catalyst component for olefin polymerization.

Example 11

(60) Preparation of Solid Component (a1):

(61) 10 g of the alkoxy magnesium support prepared in Preparatory Example, 50 mL of toluene and 2.5 mL of di-n-butyl phthalate were formulated into a suspension. In a 300 mL reaction kettle which had been repetitively purged with highly pure nitrogen gas, 40 mL of toluene and 60 mL of titanium tetrachloride were added, and then the formulated suspension was added. The reaction kettle was heated up to 80 C., kept at this temperature for 1 hour, then continuously heated up to 115 C., and kept at this temperature for 2 hours. Thereafter, the liquid (mother liquor) was filtered thoroughly. Then, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added to the resulting solid, and heated up to 110 C. to carry out treatment with stirring for 1 hour (titanium treatment). The treatment was repeated for three times. Thereafter, the liquid was filtered off, and the resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times. After filtering off the liquid, the resulting solid was dried to give a solid component (a1) of the present invention. The resulting solid component (a1) had a content of titanium of 2.4 wt %.

(62) Preparation of Catalyst Component (a11) for Olefin Polymerization:

(63) In a 300 mL reaction kettle, 10 g of the solid component (a1) and 80 mL of n-heptane were added with stirring to form a suspension. The suspension was cooled down to 0 C., to which 3 mL of triethyl silane was added, heated up to 70 C., kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-heptane at 50 C. for 4 times, the liquid was filtered off and the resulting product was dried to give a catalyst component (A11) for olefin polymerization. The catalyst component (A11) for olefin polymerization had a content of titanium atoms of 2.0 wt %, and a content of silicon atoms of 0.080 wt %.

(64) Preparation of Polyolefin:

(65) In a 5 L autoclave which had been sufficiently purged with gas phase propylene, 5 mL of a solution of triethylaluminum in hexane (concentration of triethylaluminum: 0.5 mol/L), 1 mL of a solution of cyclohexylmethyl dimethoxysilane (CHMMS) in hexane (concentration of CHMMS: 0.1 mol/L), 10 mL of anhydrous hexane and 6-10 mg of the catalyst component (A11) for olefin polymerization as above prepared were added at room temperature. The autoclave was closed, to which 0.2 standard liters (NL) of hydrogen gas and 2 L of liquid propylene were introduced. With stirring, the temperature was raised up to 70 C. within 15 minutes. After polymerization at 70 C. for 1-3 hours, the stirring was stopped, the remnant propylene monomer was removed, and the resulting product was collected as a polymer P. The results as to the polymerization activity of the catalyst component (A11) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

(66) The polymerization activity of the catalyst was calculated according to the following formula:
Polymerization activity=mass of the polymer P (kg)/mass (g) of the catalyst component (A11) for olefin polymerization.

Example 12

(67) Preparation of Catalyst Component (A12) for Olefin Polymerization:

(68) In a 300 mL reaction kettle, 10 g of the solid component (a1) prepared in Example 11 and 100 mL of n-hexane were added with stirring to form a suspension. The suspension was heated up to 60 C., to which 3 mL of triisopropyl silane was added, and kept at this temperature for 2 hours. Then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A12) for olefin polymerization. The catalyst component (A12) for olefin polymerization had a content of titanium atoms of 2.1 wt %, and a content of silicon atoms of 0.080 wt %.

(69) Preparation of Polyolefin:

(70) A12 was used in place of A11 to carry out the polymerization according to the preparation process of polyolefin described in Example 11. The results as to the polymerization activity of the catalyst component (A12) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

Example 13

(71) Preparation of Catalyst Component (A13) for Olefin Polymerization:

(72) In a 300 mL reaction kettle, 10 g of the solid component (a1) prepared in Example 11 and 50 mL of n-hexane were added with stirring to form a suspension. The suspension was heated up to 60 C., to which 3 mL of trihexyl silane was added, and kept at this temperature for 2 hours. Then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A13) for olefin polymerization. The catalyst component (A13) for olefin polymerization had a content of titanium atoms of 2.0 wt %, and a content of silicon atoms of 0.050 wt %.

(73) Preparation of Polyolefin: A13 was used in place of A11 to carry out the polymerization according to the preparation process of polyolefin described in Example 11. The results as to the polymerization activity of the catalyst component (A13) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

Example 14

(74) Preparation of Catalyst Component (A14) for Olefin Polymerization:

(75) In a 300 mL reaction kettle, 10 g of the solid component (a1) prepared in Example 11 and 100 mL of n-hexane were added with stirring to form a suspension. The suspension was cooled down to 0 C., to which 3 mL of diphenyl silane was added. The reaction solution was heated up to 60 C. within 30 minutes, kept at this temperature for 2 hours, and then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A14) for olefin polymerization. The catalyst component (A14) for olefin polymerization had a content of titanium atoms of 2.1 wt %, and a content of silicon atoms of 0.120 wt %.

(76) Preparation of Polyolefin:

(77) A14 was used in place of A11 to carry out the polymerization according to the preparation process of polyolefin described in Example 11. The results as to the polymerization activity of the catalyst component (A14) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

Example 15

(78) Preparation of Catalyst Component (A15) for Olefin Polymerization:

(79) In a 300 mL reaction kettle, 10 g of the solid component (a1) prepared in Example 11 and 100 mL of n-hexane were added with stirring to form a suspension. The suspension was heated up to 60 C., to which 0.5 mL of triethyl silane was added, and kept at this temperature for 2 hours. Then the liquid was filtered off thoroughly. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times, the liquid was filtered off, and the resulting product was dried to give a catalyst component (A15) for olefin polymerization. The catalyst component (A15) for olefin polymerization had a content of titanium atoms of 2.2 wt %, and a content of silicon atoms of 0.040 wt %.

(80) Preparation of Polyolefin:

(81) A15 was used in place of A11 to carry out the polymerization according to the preparation process of polyolefin described in Example 11. The results as to the polymerization activity of the catalyst component (A15) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

Example 16

(82) Preparation of Catalyst Component (A16) for Olefin Polymerization:

(83) 10 g of alkoxy magnesium support prepared in Preparatory Example, 50 mL of toluene and 2.5 mL of di-n-butyl phthalate were formulated into a suspension. In a 300 mL reaction kettle which had been repetitively purged with highly pure nitrogen gas, 40 mL of toluene and 60 mL of titanium tetrachloride were added. Then the formulated suspension was added into the kettle. The reaction kettle was heated up to 80 C., kept at this temperature for 1 hour, then continuously heated up to 115 C., and kept at this temperature for 2 hours. Thereafter, the liquid (mother liquor) was filtered thoroughly. Then, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added to the resulting solid, and heated up to 110 C. to carry out treatment with stirring for 1 hour, and then the liquid was filtered off. The treatment was repeated for two times. Thereafter, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added, and heated up to 110 C., to which 1.5 mL of triethyl silane was added with stirring, and kept at this temperature to carry out treatment with stirring for 1 hour, and then the liquid was filtered off. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 4 times. After filtering off the liquid, the resulting solid was dried to give a catalyst component (A16) for olefin polymerization. The catalyst component (A16) for olefin polymerization had a content of titanium atoms of 2.9 wt %, and a content of silicon atoms of 0.210 wt %.

(84) Preparation of Polyolefin:

(85) A16 was used in place of A11 to carry out the polymerization according to the preparation process of polyolefin described in Example 11. The results as to the polymerization activity of the catalyst component (A16) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

Example 17

(86) Preparation of Catalyst Component (A17) for Olefin Polymerization:

(87) 10 g of alkoxy magnesium support prepared in Preparatory Example, 50 mL of toluene and 2.5 mL of di-n-butyl phthalate were formulated into a suspension. In a 300 mL reaction kettle which had been repetitively purged with highly pure nitrogen gas, 30 mL of toluene and 120 mL of titanium tetrachloride were added. Then the formulated suspension was added. The reaction kettle was heated up to 80 C., kept at this temperature for 1 hour, then continuously heated up to 115 C., and kept at this temperature for 2 hours. Thereafter, the liquid (mother liquor) was filtered thoroughly. Then, a mixture of 120 mL of toluene and 30 mL of titanium tetrachloride was added to the resulting solid, and heated up to 110 C. to carry out treatment with stirring for 1 hour, and then the liquid was filtered off. The treatment was repeated for three times. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 2 times. Then 120 ml of hexane was added, and heated up to 60 C., to which 3 mL of triethyl silane was added with stirring, and the mixture was kept at this temperature for 2 hours, and then the liquid was filtered off. The resulting solid was washed with 120 mL of n-hexane at 50 C. for 2 times. After filtering off the liquid, the resulting solid was dried to give a catalyst component (A17) for olefin polymerization. The catalyst component (A17) for olefin polymerization had a content of titanium atoms of 2.0 wt %, and a content of silicon atoms of 0.080 wt %.

(88) Preparation of Polyolefin:

(89) A17 was used in place of A11 to carry out the polymerization according to the preparation process of polyolefin described in Example 11. The results as to the polymerization activity of the catalyst component (A17) for olefin polymerization, the melt index (MI) of the polymer, the isotacticity (II) of the polymer and the bulk density (BD) of the polymer were shown in Table 2.

Example 18

(90) Liquid Phase Bulk Polymerization of 1-Butene:

(91) In a 2 L autoclave which had been sufficiently purged with 1-butene, 2 mL of a solution of triethylaluminum in hexane (concentration of triethylaluminum: 0.5 mmol/mL), 0.5 mL of a solution of diisopropyl dimethoxysilane in hexane (concentration: 0.1 mmol/mL), 10 mL of anhydrous hexane and 10 mg of the catalyst component (A11) for olefin polymerization prepared in Example 11 were added at room temperature. The autoclave was closed, to which 2 standard liters (NL) of hydrogen gas and 350 g of liquid 1-butene were introduced. With stirring, the temperature was raised up to 60 C. within 15 minutes. After polymerization at 60 C. for 1-3 hours, the stirring was stopped, the remnant 1-butene monomer was removed, and the resulting product was collected as a polymer.

(92) The results as to the 1-butene polymerization activity of the catalyst component (A11) for olefin polymerization, and the melt index (MI) of the polymer were shown in Table 2.

(93) TABLE-US-00002 TABLE 2 Polymerization activity (Kg .Math. polymer/g .Math. Cat) MI II BD 1 hour 2 hours 3 hours (g/10 min) (%) g/cm.sup.3 Example 11: 46 89 115 6.0 98.4 0.44 A11 Example 12: 42 79 112 5.8 98.6 0.45 A12 Example 13: 41 74 103 5.2 98.2 0.44 A13 Example 14: 43 76 100 5.1 98.2 0.44 A14 Example 15: 42 75 105 5.4 98.6 0.44 A15 Example 16: 50 90 120 10.0 97.8 0.43 A16 Example 17: 48 88 113 6.0 98.4 0.44 A17 Comparative 45 69 87 5.4 98.6 0.42 Example 1: a1 Example 18: 14 26 34 1.2 A11 Comparative 15 22 29 0.9 Example 3: a1 Notes: 1, 2 and 3 hours in the table refer to that the olefin polymerization reaction, in three experiments, had been carried out for 1 hour, 2 hours and 3 hours respectively. MI, II (isotacticity) and BD values in the table were all the measured results of the polymer samples taken from one hour polymerization in various examples.

(94) As can be seen from the data in Table 2, the catalyst for olefin polymerization, which was prepared by using the catalyst component for olefin polymerization that had been treated by contacting with the SiH containing organosilicon compound (b3), could release activity more steadily and evenly, have better hydrogen response and significantly improved total activity, and could result in polymer having increased bulk density, as compared with the catalyst for olefin polymerization which was prepared by using an untreated catalyst component for olefin polymerization.