METALLOCENE COMPOUND, AND PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

Abstract

A metallocene compound having a structure shown by formula (I). A functional group connected to a bridging atom of the metallocene compound is an amine-substituted group and/or a metallocene-substituted group and/or a substituted metallocene group. A metallocene catalyst containing the metallocene compound has high catalytic activity, and can synthesize metallocene polypropylene having high isotacticity.

R.sup.IR.sup.IIZ(Cp.sup.III).sub.n(E).sub.2-nML.sup.IVL.sup.V   (I)

Claims

1. A metallocene compound, having a structure as shown in formula (I):
R.sup.IR.sup.IIZ(Cp.sup.III).sub.n(E).sub.2-nML.sup.IVL.sup.V   formula (I) wherein in formula (I), R.sup.I and R.sup.II are the same or different, and at least one of R.sup.I and R.sup.II is selected from amino-substituted C.sub.1-C.sub.20 hydrocarbyl, amino-substituted C.sub.1-C.sub.20 halohydrocarbyl, amino-substituted C.sub.1-C.sub.20 alkoxy, and amino-substituted C.sub.6-C.sub.20 phenolic group; and/or at least one of R.sup.I and R.sup.II is selected from metallocene group-substituted C.sub.1-C.sub.20 hydrocarbyl, metallocene group-substituted C.sub.1-C.sub.20 halohydrocarbyl, metallocene group-substituted C.sub.1-C.sub.20 alkoxy, and metallocene group-substituted C.sub.6-C.sub.20 phenolic group; and/or at least one of R.sup.I and R.sup.II is selected from metallocene group substituted by C.sub.1-C.sub.20 hydrocarbyl, C.sub.1-C.sub.20 halohydrocarbyl, C.sub.1-C.sub.20 alkoxy or C.sub.6-C.sub.20 phenolic group; Z is selected from carbon, silicon, germanium, and tin; Cp.sup.III is cyclopentadienyl containing or not containing a substituent, indenyl containing or not containing a substituent, or fluorenyl containing or not containing a substituent, as shown in formula (II), wherein R.sup.i, R.sup.ii, and R.sup.iii are substituents in the corresponding rings; ##STR00018## R.sup.i, R.sup.ii and R.sup.iii are the same or different, and each independently selected from hydrogen, and linear or branched, saturated or unsaturated C.sub.1-C.sub.20 hydrocarbyl with or without a heteroatom; E is NR.sup.iv or PR.sup.iv; R.sup.iv is selected from hydrogen and linear or branched, saturated or unsaturated C.sub.1-C.sub.20 hydrocarbyl with or without a heteroatom; M is selected from IVB group metals; L.sup.IV and L.sup.V are the same or different, and each independently selected from hydrogen and linear or branched, saturated or unsaturated C.sub.1-C.sub.20 hydrocarbyl with or without a heteroatom; and n is 1 or 2.

2. The metallocene compound according to claim 1, wherein the amino is as shown in formula (III): ##STR00019## wherein in formula (III), R.sub.a and R.sub.b are the same or different, and each independently selected from hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.20 arylalkyl, and C.sub.7-C.sub.20 alkylaryl, preferably from C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.12 aryl, and C.sub.7-C.sub.10 arylalkyl, more preferably from C.sub.1-C.sub.4 alkyl, phenyl, and C.sub.7-C.sub.9 arylalkyl; and/or the metal in the metallocene group is Fe, preferably, the metallocene group is ferrocenyl.

3. The metallocene compound according to claim 1, wherein in formula (I), R.sup.I and R.sup.II are the same or different, and at least one of R.sup.I and R.sup.II is selected from amino-substituted C.sub.1-C.sub.10 hydrocarbyl, amino-substituted C.sub.1-C.sub.10 halohydrocarbyl, amino-substituted C.sub.1-C.sub.10 alkoxy, and amino-substituted C.sub.6-C.sub.10 phenolic group; and/or at least one of R.sup.I and R.sup.II is selected from metallocene group-substituted C.sub.1-C.sub.10 hydrocarbyl, metallocene group-substituted C.sub.1-C.sub.10 halohydrocarbyl, metallocene group-substituted C.sub.1-C.sub.10 alkoxy, and metallocene group-substituted C.sub.6-C.sub.10 phenolic group; and/or at least one of R.sup.I and R.sup.II is selected from metallocene group substituted by C.sub.1-C.sub.10 hydrocarbyl, C.sub.1-C.sub.10 halohydrocarbyl, C.sub.1-C.sub.10 alkoxy or C.sub.6-C.sub.10 phenolic group; and/or in formula (II), R.sup.i, R.sup.ii and R.sup.iii are the same or different, and each independently selected from hydrogen, C.sub.1-C.sub.20 hydrocarbyl, C.sub.1-C.sub.20 haloalkyl, C.sub.6-C.sub.20 aryl, C.sub.6-C.sub.20 haloaryl, C.sub.7-C.sub.40 arylalkyl, C.sub.7-C.sub.40 alkylaryl, C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 heterocycloalkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.1-C.sub.20 alkoxy, C.sub.6-C.sub.20 phenolic group, C.sub.1-C.sub.20 amino, and a group containing a heteroatom selected from groups 13 to 17; and/or R.sup.iv is selected from hydrogen and linear or branched, saturated or unsaturated C.sub.1-C.sub.10 hydrocarbyl with or without a heteroatom; and/or in formula (I), M is selected from Ti, Zr and Hf; and/or in formula (I), L.sup.IV and L.sup.V are the same and selected from hydrogen, chlorine, ethyl, phenyl, benzyl, and dimethylamino.

4. A preparation method of the metallocene compound of claim 1, wherein when n is 2, the preparation method comprises: S1. reacting a H.sub.2(Cp.sup.III) with an alkali metal-organic compound to form a corresponding [H(Cp.sup.III)].sup.− alkali metal salt; S2. reacting the [H(Cp.sup.III)].sup.− alkali metal salt with a R.sup.IR.sup.IIZX.sub.2 to form a R.sup.IR.sup.IIZ[H(Cp.sup.III)].sub.2; S3. reacting the R.sup.IR.sup.IIZ[H(Cp.sup.III)].sub.2 with an alkali metal-organic compound to form a corresponding R.sup.IR.sup.IIZ(Cp.sup.III).sub.2.sup.2− alkali metal salt; S4. reacting the R.sup.IR.sup.IIZ(Cp.sup.III).sub.2.sup.2− alkali metal salt with an X.sub.2ML.sup.IVL.sup.V for salt elimination reaction, to obtain a R.sup.IR.sup.IIZ(Cp.sup.III).sub.2ML.sup.IVL.sup.V; and when n is 1, the preparation method comprises: S1. reacting a H.sub.2(Cp.sup.III) and a H.sub.2(E) with an alkali metal-organic compound respectively, to form a corresponding [H(Cp.sup.III)].sup.− alkali metal salt and a corresponding [H(E)].sup.− alkali metal salt; S2. reacting the [H(Cp.sup.III)].sup.− alkali metal salt and the [H(E)].sup.− alkali metal salt with a R.sup.IR.sup.IIZX.sub.2 to form a R.sup.IR.sup.IIZ[H(Cp.sup.III)][H(E)]; S3. reacting the R.sup.IR.sup.IIZ[H(Cp.sup.III)][H(E)] with an alkali metal-organic compound to form a corresponding R.sup.IR.sup.IIZ(Cp.sup.III)(E).sup.2− alkali metal salt; S4. reacting the R.sup.IR.sup.IIZ(Cp.sup.III)(E).sup.2− alkali metal salt with an X.sub.2ML.sup.IVL.sup.V for salt elimination reaction, to obtain a R.sup.IR.sup.IIZCp.sup.III EML.sup.IVL.sup.V; wherein X is selected from Cl, Br and I; preferably, in S4, the R.sup.IR.sup.IIZ(Cp.sup.III).sub.2.sup.2− alkali metal salt or R.sup.IR.sup.IIZ(Cp.sup.III)(E).sup.2− alkali metal salt, without separation, directly reacts with the X.sub.2ML.sup.IVL.sup.V for salt elimination reaction.

5. A preparation method of the metallocene compound of claim 1, comprising: preparing the metallocene compound by carrying out a Z hydrogenation reaction between a precursor R.sup.IHZ(Cp.sup.III).sub.n(E).sub.2-nML.sup.IVL.sup.V and a precursor of the R.sup.II; wherein the precursor of the R.sup.II is a molecule containing a multiple bond, preferably, the molecule containing a multiple bond is selected from organic multiple bond molecules, CO and CO.sub.2, wherein the multiple bond is selected from Groups 13 to 16 elements of the same or different atoms, preferably is one or more bonds of C═C, C═C, C═N, C═N, C═O, C═P, N═N, C═S, C═C═C, C═C═N, C═C═O, and N═C═N.

6. The preparation method according to claim 5, wherein the Z hydrogenation reaction is carried out in the presence of a catalyst, and the catalyst is selected from one or more of transition metal catalysts and Lewis acid catalysts, and preferably, one or more of platinum catalysts of the transition metal catalysts and B(C.sub.6F.sub.5).sub.3 catalysts of the Lewis acid; and/or, an amount of the catalyst used in the Z hydrogenation reaction is 0.00001-50%, preferably 0.01-20% of the total mass of the reactants; and/or, a temperature of the Z hydrogenation reaction is −30 to 140° C., preferably 0 to 90° C.; and/or, a reaction time of the Z hydrogenation reaction is greater than 0.1 h, preferably 2-50 h; and/or, the obtained precursor is separated or purified by recrystallization, and a solvent for the recrystallization is an aprotic solvent; preferably, the solvent is one or more selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbons, halogenated hydrocarbon compounds, ether compounds, and cyclic ether compounds; further preferably one or more of toluene, xylene, hexane, heptane, cyclohexane, and methylcyclohexane.

7. The preparation method according to claim 5, wherein the precursor R.sup.IHZ(Cp.sup.III).sub.n(E).sub.2-nML.sup.IVL.sup.V is prepared by one-pot method of chemical reaction; preferably, when n is 2, the preparation method of the precursor R.sup.IHZ(Cp.sup.III).sub.n(E).sub.2-nML.sup.IVL.sup.V comprises: step 1), reacting a H.sub.2(Cp.sup.III) with an alkali metal-organic compound to form a corresponding [H(Cp.sup.III)].sup.− alkali metal salt; step 2), reacting the [H(Cp.sup.III)] alkali metal salt with a R.sup.IHZX.sub.2 to form a R.sup.IHZ[H(Cp.sup.III)].sub.2; step 3), directly reacting the R.sup.IHZ[H(Cp.sup.III)].sub.2 without separation, with a L.sup.viiiL.sup.vivML.sup.IVL.sup.V for eliminating a stable small molecule L.sup.viii or L.sup.viv, to obtain the precursor R.sup.IHZ(Cp.sup.III).sub.2ML.sup.IVL.sup.V; and/or, directly reacting the R.sup.IHZ[H(Cp.sup.III)].sub.2 without separation, with an alkali metal-organic compound to form an alkali metal salt; the obtained alkali metal salt is then reacted with an X.sub.2ML.sup.IVL.sup.V for salt elimination reaction, to obtain the precursor R.sup.IHZ(Cp.sup.III).sub.2ML.sup.IVL.sup.V; and when n is 1, the preparation method of the precursor R.sup.IHZ(Cp.sup.III).sub.n(E).sub.2-nML.sup.IVL.sup.V comprises: step 1), reacting a H.sub.2(Cp.sup.III) and a H.sub.2(E) respectively with an alkali metal-organic compound to form a corresponding [H(Cp.sup.III)].sup.− alkali metal salt and a corresponding [H(E)] alkali metal salt; step 2), reacting the [H(Cp.sup.III)].sup.− alkali metal salt and the [H(E)].sup.− alkali metal salt with R.sup.IHZX.sub.2 to form a R.sup.IHZ[H(Cp.sup.III)][H(E)]; step 3), directly reacting the R.sup.IHZ[H(Cp.sup.III)][H(E)] without separation, with a L.sup.viiiL.sup.vivML.sup.IVL.sup.V by eliminating a stable small molecule L.sup.viii or L.sup.viv, to obtain the precursor R.sup.IHZCp.sup.IIIEML.sup.IVL.sup.V; and/or, directly reacting the R.sup.IHZ[H(Cp.sup.III)][H(E)] without separation, with an alkali metal-organic compound to form an alkali metal salt; then reacting the obtained alkali metal salt with a X.sub.2ML.sup.IVL.sup.V for salt elimination reaction, to obtain the precursor R.sup.IHZCp.sup.IIIEML.sup.IVL.sup.V; wherein X is selected from Cl, Br and I.

8. The preparation method according to claim 4, wherein in each step, a reaction temperature of the reaction is in a range from −100° C. to 140° C., preferably in a range from −85° C. to 110° C.; and/or, and a reaction time is more than 0.016 h, preferably 2 to 100 h; preferably, in each step, reaction materials are mixed at a temperature of −100° C. to −20° C., preferably −85° C. to −10° C., and the mixed reaction materials are reacted at 10° C. to 50° C., preferably at 20° C. to 35° C. for 1 h to 100 h, preferably 5 h to 50 h.

9. The preparation method according to claim 4, wherein in each step, the reaction is carried out in an aprotic solvent selected from one or more of linear or branched alkane compounds, cycloalkane compounds, aromatic compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably one or more of toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether, and dioxane; and/or the alkali metal-organic compound is selected from hydrogenated metal, alkyl metal, alkenyl metal, aromatic metal, and amine metal, preferably alkyl metal, more preferably C.sub.1-C.sub.6 alkyl metal; and/or, the alkali metal is selected from Li, Na and K, preferably Li.

10. A catalyst for α-olefin polymerization reaction, comprising: the metallocene compound of claim 1, a cocatalyst, and a carrier.

11. The catalyst according to claim 10, wherein the cocatalyst is selected from one or more of a Lewis acid, and an ionic compound containing a non-coordination anion and a Lewis acid or containing a non-coordination anion and a Bronsted acid cation; preferably, the Lewis acid comprises one or more of alkyl aluminum, alkyl aluminoxane, and organic borides; and/or the ionic compound containing a non-coordination anion and a Lewis acid or containing a non-coordination anion and a Bronsted acid cation is selected from compounds containing 1-4 perfluoroaryl substituted borate anions.

12. The catalyst according to claim 11, wherein the alkyl aluminum comprises trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum, tri-isoamyl aluminum, tri-n-amyl aluminum, tri-isohexyl aluminum, tri-n-hexyl aluminum, tri-isoheptyl aluminum, tri-n-heptyl aluminum, tri-isooctyl aluminum, tri-n-octyl aluminum, tri-isononyl aluminum, tri-n-nonyl aluminum, tri-isodecyl aluminum and tri-n-decyl aluminum; and/or the alkyl aluminoxane comprises methyl aluminoxane, ethyl aluminoxane and butyl modified aluminoxane; and/or the organic boride comprises trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (pentafluorophenyl) borane, tris (3,5-difluorophenyl) borane and tris (2,4,6-trifluorophenyl) borane; and/or the perfluoroaryl group is selected from perfluorophenyl, perfluoronaphthyl, perfluoro biphenyl, and perfluoroalkyl phenyl, and the cation is selected from n, n-dimethylphenylammonium ion, triphenylcarboonium ion, trialkyl ammonium ion, and triarylammonium ion.

13. The catalyst according to claim 10, wherein in the catalyst, a content of the metallocene compound, calculated based on the M element, is 0.001 mass % to 10 mass %, preferably 0.01 mass % to 1 mass %; and/or a molar ratio of Al element in the cocatalyst and M element in the metallocene compound is (1 to 500):1, preferably (50 to 300):1.

14. A preparation method of the catalyst according to claim 10, comprises: combining the metallocene compound, the cocatalyst, and the carrier under the action of a solvent to form the catalyst, and preferably, a combining condition comprises: a combining temperature being −40° C. to 200° C., preferably 40° C. to 120° C.; a combining time being greater than 0.016 h, preferably 2 h to 100 h.

15. The preparation method according to claim 14, wherein the solvent is selected from one or more of linear hydrocarbons, branched hydrocarbons, cyclic saturated hydrocarbons and aromatic hydrocarbons, preferably one or more of toluene, xylene, n-butane, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane and neoheptane.

16. A method for α-olefin polymerization carried out in the presence of the metallocene compound according to claim 1.

17. The method according to claim 16, wherein the polymerization reaction is carried out without a solvent.

18. The method according to claim 16, wherein conditions of the polymerization reaction comprises: reaction temperature being −50° C. to 200° C., preferably 30° C. to 100° C.; and the reaction time being 0.01 h to 60 h, preferably 0.1 h to 10 h, and/or, wherein relative to per gram of α-olefin, the usage of the metallocene catalyst or metallocene catalyst system is 0.001 mg to 1000 mg, preferably 0.01 mg to 200 mg, more preferably 0.1 mg to 20 mg, and/or, wherein the α-olefin comprises C2-C20 α-olefin, preferably C2-C14 α-olefin, more preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-heptadiene, 1-octadecene and 1-eicosene, preferentially 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene or 1-tetradecene.

19-20. (canceled)

21. The preparation method according to claim 7, wherein in each step, a reaction temperature of the reaction is in a range from −100° C. to 140° C., preferably in a range from −85° C. to 110° C.; and/or, and a reaction time is more than 0.016 h, preferably 2 to 100 h; preferably, in each step, reaction materials are mixed at a temperature of −100° C. to −20° C., preferably −85° C. to −10° C., and the mixed reaction materials are reacted at 10° C. to 50° C., preferably at 20° C. to 35° C. for 1 h to 100 h, preferably 5 h to 50 h.

22. The preparation method according to claim 7, wherein in each step, the reaction is carried out in an aprotic solvent selected from one or more of linear or branched alkane compounds, cycloalkane compounds, aromatic compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably one or more of toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether, and dioxane; and/or the alkali metal-organic compound is selected from hydrogenated metal, alkyl metal, alkenyl metal, aromatic metal, and amine metal, preferably alkyl metal, more preferably C.sub.1-C.sub.6 alkyl metal; and/or, the alkali metal is selected from Li, Na and K, preferably Li.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0143] The present disclosure will be further illustrated by the following examples.

[0144] In the following embodiments, unless otherwise specified, the aluminum/zirconium ratio is the molar ratio of aluminum to zirconium.

[0145] In the present disclosure, unless otherwise specified, the Al/Zr ratio refers to the molar ratio of Al element to Zr element.

[0146] In the present disclosure, unless otherwise specified, “%” means mass percentage.

[0147] In the present disclosure, the calculation formula of polymerization activity is: Polymerization activity=quality of polymerized product/(polymerization time×catalyst amount×zirconium content).

A. Preparation of Metallocene Compounds

Synthesis Example 1

[0148] Preparation of the metallocene compound as shown in formula 1:

[0149] 40 mmol of 4-phenyl-2-methylindene was weighed and dissolved in 200 mL of Et.sub.2O, and cooled to −78° C. 40 mmol of n-butyllithiumin in a hexane solution with a concentration of 2.4M was slowly dropwise added into the resulting mixture over 15 min. After the addition was completed, the mixture was naturally warmed to room temperature under stirring, and stirred for another 12 hours at room temperature to obtain a solution of indenyl lithium compound.

[0150] 20 mmol of Me(PhMeNH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2 was weighed and dissolved in 100 mL of n-hexane, and cooled to −78° C. The solution of indenyl lithium compound prepared above was slowly dropwise added into the resulting mixture over 30 minutes. Then the mixture was naturally warmed to room temperature under stirring, and stirred for another 12 h at room temperature. The insoluble matter was removed by filtration, and the filtrate was passed through a silica gel column to obtain a yellow solution. The solvent was drained to obtain a yellow compound Me(PhMeNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.5).sub.2, which was weighed 8.2 mmol, and the yield was 41%.

[0151] 5 mmol of Me(PhMeNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.5).sub.2 was weighed and dissolved in 100 mL THF, and cooled to −78° C. 10 mmol of n-butyllithiumin in a hexane solution with a concentration of 2.4M was slowly dropwise added into the resulting mixture over 15 minutes. The resulting mixture was naturally warmed to room temperature under stirring, and stirred at room temperature for another 12 hours to obtain a solution of silicon-bridged indenyl lithium compound.

[0152] 5 mmol ZrCl.sub.4 was weighed and added into 100 mL THF, and cooled to −78° C. With stirring, the solution of silicon-bridged indenyl lithium compound prepared above was slowly dropwise added into the resulting mixture over 15 minutes. The resulting mixture was then naturally warmed to room temperature under stirring, and stirred for another 12 h at room temperature. The insoluble matter was removed by filtration, the filtrate was collected, and the THF solvent in the filtrate was removed. The remaining solid was extracted with 100 mL of toluene. The extraction solution was crystallized at −20° C. to obtain an orange-red zirconocene compound [Me(PhMeNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2]ZrCl.sub.2 as shown in formula 1, which was weighed 1.2 mmol, and the yield was 24%.

[0153] The preparation methods of the metallocene compounds of formula 2 to formula 11 were similar to this, except that, Me(PhMeNH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2 in the second step was replaced with Me(PhMeNH.sub.2CH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(Me.sub.2NH.sub.2CH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(Me.sub.2NH.sub.2CH.sub.2C)SiCl.sub.2, Me(Me.sub.2NH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(NH.sub.2Pr.sub.2NH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(iPr.sub.2NH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(iBuMeNH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(iBuEtNH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, Me(iPrEtNH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2, (Me.sub.2NH.sub.2CH.sub.2C)(iBuMeNH.sub.2CH.sub.2CH.sub.2C)SiCl.sub.2 respectively, finally to obtain zirconocene compounds Me(PhMeNH.sub.2CH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 2, which was weighed 1.0 mmol, yield 20%), Me(Me.sub.2NH.sub.2CH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 3, which was weighed 1.4 mmol, yield 28%), Me(Me.sub.2NH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2(formula 4, which was weighed 1.2 mmol, yield 24%), Me(Me.sub.2NH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 5, which was weighed 1.0 mmol, yield 20%), Me(NH.sub.2Pr.sub.2NH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 6, which was weighed 1.3 mmol, yield 26%), Me(iPr.sub.2NH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 7, which was weighed 1.0 mmol, yield 20%), Me(iBuMeNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 8, which was weighed 0.9 mmol, yield 18%), Me(iBuEtNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 9, which was weighed 0.8 mmol, yield 16%), Me(iPrEtNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 10, which was weighed 0.9 mmol, yield 18%), (Me.sub.2NH.sub.2CH.sub.2C)(iBuMeNH.sub.2CH.sub.2CH.sub.2C)Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 11, which was weighed 0.6 mmol, yield 12%) respectively.

[0154] The preparation methods of the metallocene compound of formula 12 to formula 14 were also the similar to this, except that Me(PhMeNCH.sub.2CH.sub.2CH.sub.2)SiCl.sub.2 in the second step was replaced with Me[CpFe(C.sub.5H.sub.4)CH.sub.2CH.sub.2]SiCl.sub.2, Me[CpFe(C.sub.5H.sub.4)CH.sub.2CH.sub.2CH.sub.2]SiCl.sub.2, Me[CpFe(C.sub.5H.sub.4)CH.sub.2]SiCl.sub.2 respectively, and finally zirconocene compounds Me[CpFe(C.sub.5H.sub.4)CH.sub.2CH.sub.2]Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 12, which was weighed 1.0 mmol, yield 20%), Me[CpFe(C.sub.5H.sub.4)CH.sub.2CH.sub.2CH.sub.2]Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 13, which was weighed 1.3 mmol, yield 26%), Me[CpFe(C.sub.5H.sub.4)CH.sub.2]Si(4-Ph-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 14, which was weighed 0.8 mmol, yield 16%) were obtained.

[0155] The preparation methods of the metallocene compound of formula 15 was the similar to this, except that, 4-phenyl-2-methyl indenyl in the first step was replaced with 4-(4-tert butyl)phenyl-2-methyl indenyl, and in the meantime, Me(PhMeNCH.sub.2CH.sub.2CH.sub.2)SiCl.sub.2 in the second step was replaced with Me[CpFe(C.sub.5H.sub.4)CH.sub.2CH.sub.2]SiCl.sub.2, finally to obtain zirconocene compound Me[CpFe(C.sub.5H.sub.4)CH.sub.2CH.sub.2]Si(4-(4-tBuC.sub.6H.sub.4)-2-MeC.sub.9H.sub.4).sub.2ZrCl.sub.2 (formula 15, which was weighed 1.0 mmol, yield 20%).

Synthesis Examples 2-12 Preparation of Precursor

Preparation of Hydrogen Silicon Bridged Bisindenyl Zirconocene Compound MeHSi(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(MS-1)

[0156] 2-methyl-7-p-tert-butylphenylindene (5.24 g, 20 mmol) was weighed and dissolved in Tol (80 mL) solvent. N-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the mixture at −78° C., gradually warmed to room temperature and reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly dropwise added into the mixture at −78° C., and gradually warmed to room temperature and stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was placed at −78° C., and n-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the mixture. After warmed to room temperature, stirring was continued for 2 h to obtain an orange-yellow turbid solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was put into a vial. followed by adding 40 mL of toluene, and being placed under the nitrogen protection, and was added into the above yellow turbid liquid at room temperature. Soon the color would gradually darken from orange-yellow to brown-black. Reaction was carried out for 1 day. The reaction solution was filtered under the protection of nitrogen, the obtained filtrate was drained of solvent, washed with n-hexane, filtered and drained to obtain a yellow solid. The yellow solid was recrystallized from toluene in multiple steps at −20° C. to obtain 1.76 g (24.2%) of racemic compound rac-MS-1 and 3.42 g (47.0%) of meso-MS-1 compound.

[0157] The two compounds were isomers and had the same elemental composition. One of them was selected to be elementally analyzed to confirm its composition. The composition was C.sub.41H.sub.48Cl.sub.2SiZr(Mr=731.04): theoretical value: C, 67.36; H, 6.62; measured value: C, 67.54, H, 6.56.

Synthesis Example 2

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(Me.SUB.2.NCH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1a)

[0158] Rac-MS-1 (1.45 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Me.sub.2NCH═CH.sub.2 (0.156 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, 5% dosage) were added into the mixture. The mixture was heated to 50° C. for 24 h. All the volatile components were removed by vacuuming at room temperature. The remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried under vacuum for 6 hours to obtain 1.36 g (85.2%) of yellow solid rac-MS-1a.

[0159] The composition was C.sub.45H.sub.57Cl.sub.2NSiZr(Mr=802.16): theoretical value: C, 67.38; H, 7.16; N, 1.75; measured value: C, 67.42; H, 7.19; N, 1.78.

Synthesis Example 3

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(Me.SUB.2.NCH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(meso-MS-1a)

[0160] The implementation steps were the same as Synthesis Example 2, wherein rac-MS-1 was replaced with meso-MS-1 (1.45 g, 2 mmol), and finally 1.4 g (87.7%) of yellow solid meso-MS-1a was obtained.

[0161] The compound meso-MS-1 and the above-mentioned rac-MS-1 were isomers, and the composition was also C.sub.45H.sub.57Cl.sub.2NSiZr(Mr=802.16): theoretical value: C, 67.38; H, 7.16; N, 1.75; measured value: C, 67.44; H, 7.18; N, 1.77.

Synthesis Example 4

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconium Compound Me(PhMeNCH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1b)

[0162] The implementation steps were the same as Synthesis Example 2, wherein Me.sub.2NCH═CH.sub.2 was replaced with PhMeNCH═CH.sub.2 (0.293 g, 2.2 mmol), and finally 1.65 g (95.9%) of yellow solid rac-MS-1b was obtained.

[0163] The composition was C.sub.50H.sub.59Cl.sub.2NSiZr(Mr=864.23): theoretical value: C, 69.49; H, 6.88; N, 1.62; measured value: C, 69.45; H, 6.89; N, 1.65.

Synthesis Example 5

Preparation of Aminoalkyl-Containing Silicon Bridged Bis-Indenocyl Zirconocene Compound Me(Me.SUB.2.NCH.SUB.2.CH.SUB.7.CH)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1c)

[0164] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with Me.sub.2NCH.sub.2CH═CH.sub.2 (0.187 g, 2.2 mmol), and finally 1.35 g (83.2%) of yellow solid rac-MS-1c was obtained.

[0165] The composition was C.sub.46H.sub.59Cl.sub.2NSiZr(Mr=816.18): theoretical value: C, 67.69; H, 7.29; N, 1.72; measured value: C, 67.65; H, 7.30; N, 1.70.

Synthesis Example 6

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(PhMeNCH.SUB.2.CH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1d)

[0166] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with PhMeNCH.sub.2CH═CH.sub.2 (0.324 g, 2.2 mmol), and finally 1.61 g (92.3%) of yellow solid rac-MS-1d was obtained.

[0167] The composition was C.sub.51H.sub.61Cl.sub.2NSiZr(Mr=878.25): theoretical value: C, 69.75; H, 7.00; N, 1.59; measured value: C, 69.78; H, 7.02; N, 1.60.

Synthesis Example 7

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(iPr.SUB.2.NCH.SUB.2.CH.SUB.7.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1e)

[0168] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with iPr.sub.2NCH.sub.2CH═CH.sub.2 (0.310 g, 2.2 mmol), and finally a yellow solid rac-MS-1e 1.54 g (88.8%) was obtained.

[0169] The composition was C.sub.50H.sub.67Cl.sub.2NSiZr(Mr=872.29): theoretical value: C, 68.85; H, 7.74; N, 1.61; measured value: C, 68.83; H, 7.71; N, 1.63.

Synthesis Example 8

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(iBuMeNCH.SUB.2.CH.SUB.2.CH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1f)

[0170] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with iBuMeNCH.sub.2CH.sub.2CH═CH.sub.2 (0.310 g, 2.2 mmol), and finally a yellow solid rac-MS-if 1.57 g (90.62%) was obtained.

[0171] The composition was C.sub.50H.sub.67Cl.sub.2NSiZr(Mr=872.29): theoretical value: C, 68.85; H, 7.74; N, 1.61; measured value: C, 68.82; H, 7.72; N, 1.63.

Synthesis Example 9

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(PhMeNCH.SUB.2.CH.SUB.2.CH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.12 .(rac-MS-1g)

[0172] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with PhMeNCH.sub.2CH.sub.2CH═CH.sub.2 (0.354 g, 2.2 mmol), and finally a yellow solid rac-MS-1 g 1.64 g (92.52%) was obtained.

[0173] The composition was C.sub.52H.sub.63Cl.sub.2NSiZr(Mr=892.28): theoretical value: C, 70.00; H, 7.12; N, 1.57; measured value: C, 70.04; H, 7.11; N, 1.59.

Synthesis Example 10

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(iPrEtNCH.SUB.2.CH.SUB.2.CH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1h)

[0174] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with iPrEtNCH.sub.2CH.sub.2CH═CH.sub.2 (0.310 g, 2.2 mmol), and finally a yellow solid rac-MS-1h 1.57 g (90.61%) was obtained.

[0175] The composition was C.sub.50H.sub.71Cl.sub.2NSiZr(Mr=876.32): theoretical value: C, 68.53; H, 8.17; N, 1.60; measured value: C, 68.51; H, 8.18; N, 1.62.

Synthesis Example 11

Preparation of Ferrocenylalkenyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(FcCH═CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1i)

[0176] The implementation steps were the same as Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced with FcC≡CH (0.420 g, 2 mmol), and finally an orange-red solid rac-MS-1i 1.72 g(91.98%) was obtained. In FcC≡CH, Fc=CpFe(C.sub.5H.sub.4).

[0177] The composition was C.sub.53H.sub.58Cl.sub.2FeSiZr(Mr=941.09): theoretical value: C, 67.64; H, 6.21; measured value: C, 67.71; H, 6.25.

Synthesis Example 12

Preparation of Ferrocenylalkenyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(FcCH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-1j)

[0178] The implementation steps were the same as in Example 1, wherein Me.sub.2NCH═CH.sub.2 was replaced of FcCH═CH.sub.2 (0.424 g, 2 mmol), and finally an orange-red solid rac-MS-1j 1.63 g(87.17%). In FcCH═CH.sub.2, Fc=CpFe(C.sub.5H.sub.4).

[0179] The composition was C.sub.53H.sub.60Cl.sub.2FeSiZr(Mr=943.10): theoretical value: C, 67.50; H, 6.41; measured value: C, 67.53; H, 6.43.

Synthesis Examples 13 and 14 Preparation of Precursors

Preparation of Hydrogen Silicon Bridged Bisindenyl Zirconocene Compound MeHSi(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.Zr(NMe.SUB.2.).SUB.2 .(rac-MS-2)

[0180] 2-methyl-7-p-tert-butyl phenylindene (5.24 g, 20 mmol) was weighed and dissolved in tol (160 ml) solvent. N-butyl lithium (2.4 M, 8.5 ml, 20 mmol) was slowly dropwise added into the mixture at −78° C. After gradually warmed to the room temperature, the resulting mixture was reacted overnight to obtain a wine red solution. Methyldichlorosilane (1.04 ml, 10 mmol) was slowly dropwise added into the wine red solution at 78° C., followed by gradually warming to the room temperature and stirring for more than 8 hours to obtain a yellow suspension. The yellow suspension was filtered and LiCl precipitation was removed to obtain a yellow solution. tetramethylaminozirconium (2.68 g, 10 mmol) was added into the yellow solution under stirring, and heated to 70 to 100° C. for 12 hours. When it was cooled to room temperature, the volatile components were removed, and the remaining solid was recrystallized with toluene and hexane to obtain 4.83 g (64.9%) of orange crystalline solid rac-ms-2.

[0181] The composition was C.sub.45H.sub.60N.sub.2SiZr(Mr=748.28): theoretical value: C, 72.23; H, 8.08; N, 3.74; measured value: C, 72.21; H, 8.05; N, 3.76.

Synthesis Example 13

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(PhMeNCH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.Zr(NMe.SUB.2.) (rac-MS-2a)

[0182] Rac-MS-2 (1.49 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeNCH═CH.sub.2 (0.293 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain an orange solid rac-MS-2a 1.62 g (92.2%).

[0183] The composition was C.sub.54H.sub.71N.sub.3SiZr(Mr=881.47): theoretical value: C, 73.58; H, 8.12; N, 4.77; measured value: C, 73.60; H, 8.14; N, 4.75.

Synthesis Example 14

Preparation of Ferrocenylalkenyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(FcCH.SUB.2.CH.SUB.2.)Si(2-Me-7-p-tBuC.SUB.6.H.SUB.4.C.SUB.9.H.SUB.4.).SUB.2.Zr(NMe.SUB.2.).SUB.2 .(rac-MS-2b)

[0184] The implementation steps were the same as Example 13, wherein PhMeNCH═CH.sub.2 was replaced with FcCH═CH.sub.2 (0.424 g, 2 mmol), and finally an orange-red solid meso-MS-1a 1.4 g(87.7%). In FcCH═CH.sub.2, Fc=CpFe(C.sub.5H.sub.4).

[0185] The composition was C.sub.57H.sub.72N.sub.2FeSiZr(Mr=960.35): theoretical value: C, 71.29; H, 7.56; N, 2.93; measured value: C, 71.27; H, 7.56; N, 2.91.

Synthesis Examples 15 and 16 Preparation of Precursors

Preparation of Hydrogen Silicon-Based Bridged Bisindenyl Zirconocene Compound MeHSi(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(MS-3)

[0186] 2-methyl-7-phenylindene (4.13 g, 20 mmol) was weighed and dissolved in Tol (160 mL) solvent. N-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the mixture at −78° C., gradually warmed to room temperature and reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly dropwise added into the solution at −78° C., and then gradually warmed to room temperature and stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was placed at −78° C., and n-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the suspension. After warming to room temperature, stirring was continued for 2 h to obtain an orange-yellow turbid solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was put into a vial, followed by adding 40 mL of toluene, and being placed under the nitrogen protection. Zirconium tetrachloride was added into the above yellow turbid liquid at room temperature, and soon the color would gradually darken from orange-yellow to brown-black. Reaction was carried out for 1 day. The reaction solution was filtered under the protection of nitrogen, the obtained filtrate was drained of solvent, washed with n-hexane, filtered and drained to obtain a yellow solid. The yellow solid was recrystallized from toluene in multiple steps at −20° C. to obtain 1.25 g (18.7%) of the racemic compound rac-MS-3 and 2.75 g (41.2%) of the meso-MS-3 compound.

[0187] The composition was C.sub.33H.sub.28Cl.sub.2SiZr(Mr=614.79): theoretical value: C, 64.47; H, 4.59; measured value: C, 64.48; H, 4.61.

Synthesis Example 15

Preparation of Aminoalkyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(PhMeNCH.SUB.2.CH.SUB.2.)Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-3a)

[0188] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeNCH═CH.sub.2 (0.293 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.41 g (87.4%) orange-red solid rac-MS-3a.

[0189] The composition was C.sub.42H.sub.39Cl.sub.2NSiZr(Mr=747.98): theoretical value: C, 67.44; H, 5.26; N, 1.87; measured value: C, 67.42; H, 5.27; N, 1.86.

Synthesis Example 16

Preparation of Ferrocenylalkenyl-Containing Silicon Bridged Bisindenyl Zirconocene Compound Me(FcCH.SUB.2.CH.SUB.2.)Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2 .(rac-MS-3b)

[0190] The implementation steps were the same as Synthesis Example 13, wherein PhMeNCH═CH.sub.2 was replaced with FcCH═CH.sub.2 (0.424 g, 2 mmol), and finally an orange-red solid rac-MS-3b 1.53 g (86.7%) was obtained. In FcCH═CH.sub.2, Fc=CpFe(C.sub.5H.sub.4).

[0191] The composition was C.sub.45H.sub.40Cl.sub.2FeSiZr(Mr=826.86): theoretical value: C, 65.37: H, 4.88; measured value: C, 65.36; H, 4.89.

Preparation of Precursors of Synthesis Examples 16 and 17

Preparation of Hydrogen Silicon Bridged Bisfluorenyl Zirconocene Compound MeHSiFlu.SUB.2.ZrCl.SUB.2.(MS-4)

[0192] Fluorene (3.32 g, 20 mmol) was weighed and dissolved in Tol (160 mL) solvent. N-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the mixture at −78° C. Then the resulting mixture was gradually warmed to room temperature and reacted overnight to obtain wine red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly added dropwise into the wine red solution at −78° C., and gradually warmed to room temperature and stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was placed at −78° C., and n-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into it. After warming to room temperature, stirring was continued for 2 h to obtain an orange-yellow turbid solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was put into a vial, followed by adding 40 mL of toluene, and being placed under the nitrogen protection. Zirconium tetrachloride was added into the above yellow turbid liquid at room temperature, and soon the color would gradually darken from orange-yellow to brown-black. Reaction was carried out for 1 day. The reaction solution was filtered under the protection of nitrogen, the obtained filtrate was drained of solvent, washed with n-hexane, filtered and drained to obtain a yellow solid. The yellow solid was recrystallized from toluene at −20° C. to obtain 3.89 g (72.8%) of compound MS-4.

[0193] The composition was C.sub.27H.sub.20Cl.sub.2SiZr(Mr=534.66): theoretical value: C, 60.66; H, 3.77; measured value: C, 60.64; H, 3.74.

Synthesis Example 17

Preparation of Aminoalkyl-Containing Silicon Bridged Bisferrocenyl Zirconocene Compound Me(PhMeNCH.SUB.2.CH.SUB.2.)SiFlu.SUB.2.ZrCl.SUB.2 .(MS-4a)

[0194] MS-4 (1.07 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeNCH═CH.sub.2 (0.293 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain of orange solid MS-4a 1.21 g (90.6%).

[0195] The composition was C.sub.36H.sub.3Cl.sub.2NSiZr(Mr=667.85): theoretical value: C, 64.74; H, 4.68; N, 2.10; measured value: C, 64.73; H, 4.71; N, 2.11.

Synthesis Example 18

Preparation of Ferrocenyl-Containing Alkyl Silicon Bridged Bisfluorenyl Zirconocene Compound Me(FcCH.SUB.2.CH.SUB.2.)SiFlu.SUB.2.ZrCl.SUB.2 .(MS-4b)

[0196] The implementation steps were the same as Synthesis Example 17, wherein PhMeNCH═CH.sub.2 was replaced with FcCH═CH.sub.2 (0.424 g, 2 mmol), and finally an orange-red solid MS-4b 1.32 g (88.4%) was obtained. In FcCH═CH.sub.2, Fc=CpFe(C.sub.5H.sub.4).

[0197] The composition was C.sub.39H.sub.32Cl.sub.2FeSiZr(Mr=746.73): theoretical value: C, 62.73; H, 4.32; measured value: C, 62.72; H, 4.31.

Synthesis Example 19

Preparation of Me[(PhMeN(CH.SUB.2.).SUB.5.)]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0198] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH.sub.2); CH═CH.sub.2 (0.388 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.49 g (86.2%) of orange-red solid rac-MS-3c.

[0199] The composition was C.sub.45H.sub.45Cl.sub.2NSiZr(Mr=790.97): theoretical value: C, 68.41; H, 5.74; N, 1.77; measured value: C, 68.44; H, 5.75; N, 1.76.

Synthesis Example 20

Preparation of Me[PhMeN(CH.SUB.2.).SUB.8.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0200] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH.sub.2).sub.6CH═CH.sub.2 (0.480 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.57 g (86.3%) of orange-red solid rac-MS-3d.

[0201] The composition was C.sub.48H.sub.51Cl.sub.2NSiZr(Mr=832.15): theoretical value: C, 69.28; H, 6.18; N, 1.68; measured value: C, 69.25; H, 6.16; N, 1.70.

Synthesis Example 21

Preparation of Me[PhMeN(CH.SUB.2.).SUB.12.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.)ZrCl.SUB.2

[0202] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH.sub.2).sub.9CH═CH.sub.2 (0.573 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.72 g (89.9%) of orange-red solid rac-MS-3e.

[0203] The composition was C.sub.51H.sub.57Cl.sub.2NSiZr(Mr=874.23): theoretical value: C, 70.07; H, 6.57; N, 1.60; measured value: C, 70.04; H, 6.55; N, 1.60.

Synthesis Example 22

Preparation of Me[PhMeN(CH.SUB.2.).SUB.15.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0204] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH.sub.2).sub.12CH═CH.sub.2 (0.666 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.83 g (91.2%) of orange-red solid rac-MS-3f.

[0205] The composition was C.sub.54H.sub.3Cl.sub.2NSiZr(Mr=916.31): theoretical value: C, 70.78; H, 6.93; N, 1.53; measured value: C, 70.76; H, 6.95; N, 1.52.

Synthesis Example 23

Preparation of Me[p-ClC.SUB.6.H.SUB.4.MeN(CH.SUB.2.).SUB.5.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0206] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. p-ClC.sub.6H.sub.4MeN(CH.sub.2).sub.3CH═CH.sub.2 (0.461 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.62 g (90.0%) of orange-red solid rac-MS-3 g.

[0207] The composition was C.sub.45H.sub.44Cl.sub.3NSiZr(Mr=824.51): theoretical value: C, 65.55; H, 5.38; N, 1.70; measured value: C, 65.56; H, 5.36; N, 1.72.

Synthesis Example 24

Preparation of Me[p-MeOC.SUB.6.H.SUB.4.MeN(CH.SUB.2.).SUB.5.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0208] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. p-MeOC.sub.6H.sub.4MeN(CH.sub.2).sub.3CH═CH.sub.2 (0.454 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) was added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.60 g (89.2%) of orange-red solid rac-MS-3h.

[0209] The composition was C.sub.46H.sub.46Cl.sub.2NOSiZr(Mr=819.09): theoretical value: C, 67.45; H, 5.66; N, 1.71; measured value: C, 67.47; H, 5.63; N, 1.72.

Synthesis Example 25

Preparation of Me[Fc(CH.SUB.2.).SUB.5.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0210] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH.sub.2).sub.3CH═CH.sub.2 (0.559 g, 2.2 mmol) (note: Fc=CpFe(C.sub.5H.sub.4)) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, 5% usage) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.67 g (87.9%) of orange-red solid rac-MS-3i.

[0211] The composition was C.sub.48H.sub.46Cl.sub.2FeSiZr(Mr=868.95): theoretical value: C, 66.35; H, 5.34; measured value: C, 66.36; H, 5.33.

Synthesis Example 26

Preparation of Me(Fc(CH.SUB.2.).SUB.8.)Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0212] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH.sub.2).sub.6CH═CH.sub.2 (0.652 g, 2.2 mmol)(note: Fc=CpFe(C.sub.5H.sub.4)) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, 5% usage) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.72 g (86.3%) of orange-red solid rac-MS-3j.

[0213] The composition was C.sub.51H.sub.52Cl.sub.2FeSiZr(Mr=911.03): theoretical value: C, 65.55; H, 5.38; measured value: C, 65.56; H, 5.37.

Synthesis Example 27

Preparation of Me[Fc(CH.SUB.2.).SUB.12.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0214] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH.sub.2).sub.10CH═CH.sub.2 (0.775 g, 2.2 mmol) (note: Fc=CpFe(C.sub.5H.sub.4)) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) was added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.98 g (93.6%) of orange-red solid rac-MS-3k.

[0215] The composition was C.sub.55H.sub.60Cl.sub.2FeSiZr(Mr=967.14): theoretical value: C, 68.31; H, 6.25; measured value: C, 68.34; H, 6.27.

Synthesis Example 28

Preparation of Me[Fc(CH.SUB.2.).SUB.15.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0216] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH.sub.2).sub.13CH═CH.sub.2 (0.868 g, 2.2 mmol) (note: Fc=CpFe(C.sub.5H.sub.4)) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. After vacuum drying for 6 hours, 2.02 g (91.5%) of orange-red solid rac-MS-31 was obtained.

[0217] The composition was C.sub.58H.sub.66Cl.sub.2FeSiZr(Mr=1009.22): theoretical value: C, 69.03; H, 6.59; measured value: C, 69.04; H, 6.57.

Synthesis Example 29

[0218] The metallocene compound with R.sup.I being methyl group and R.sup.II being an alkyl group can be synthesized by referring to the bridged SiH group addition method.

Preparation of MenBuSi(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0219] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. CH.sub.3CH.sub.2CH═CH.sub.2 (0.123 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) was added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. It was dried in vacuum for 6 hours to obtain 1.12 g (76.6%) of orange-red solid rac-MS-3m.

[0220] The composition was C.sub.37H.sub.36Cl.sub.2SiZr(Mr=670.90): theoretical value: C, 66.24; H, 5.41; measured value: C, 66.23; H, 5.40.

Synthesis Example 30

Preparation of Me[n-CH.SUB.3.(CH.SUB.2.).SUB.7.]Si(2-Me-7-PhC.SUB.9.H.SUB.4.).SUB.2.ZrCl.SUB.2

[0221] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. CH.sub.3(CH.sub.2).sub.5CH═CH.sub.2 (0.247 g, 2.2 mmol) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. After vacuum drying for 6 hours, 1.23 g (77.5%) of orange-red solid rac-MS-3n was obtained.

[0222] The composition was C.sub.41H.sub.44Cl.sub.2SiZr(Mr=727.01): theoretical value: C, 67.74; H, 6.10; measured value: C, 67.72; H, 6.11.

Synthesis Example 31

Preparation of MeHSi(4-Ph-2-MeC.SUB.9.H.SUB.4.)(NtBu)ZrCl.SUB.2

[0223] 4-phenyl-2-methylindene (2.06 g, 10 mmol) was weighed and dissolved in Tol (80 ml) solvent. N-butyllithium (2.4M, 4.25 mL, 10 mmol) was slowly dropwise added into the mixture at −78° C., gradually warmed to room temperature and reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly dropwise added into the wine-red solution at −78° C., after gradually warming to room temperature, stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was placed at −78° C., and lithium tert-butylamine (0.79 g, 10 mmol) was slowly dropwise added into the suspension, and the stirring was continued for 2 h after returning to room temperature to obtain an orange-yellow turbid liquid. The orange-yellow turbid liquid was placed at −78° C., and n-butyllithium (2.4M, 8.5 mL, 20 mmol) was slowly dropwise added into the liquid. After returning to room temperature, stirring was continued for 2 h to obtain an orange-yellow turbid liquid. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was put into a vial, followed by adding 40 mL of toluene, and being placed under the nitrogen protection. Zirconium tetrachloride was added into the above yellow turbid liquid at room temperature, and soon the color would gradually darken from orange-yellow to dark red. Reaction was carried out for 1 day. The reaction solution was filtered under the protection of nitrogen, the obtained filtrate was drained of solvent, washed with n-hexane, filtered and drained to obtain a red solid. The red solid was recrystallized in multiple steps at −20° C. from toluene to obtain the compound MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl.sub.2 2.88 g (60.0%).

[0224] The composition was C.sub.21H.sub.25Cl.sub.2NSiZr(Mr=481.65): theoretical value: C, 52.37; H, 5.23; N, 2.91; measured value: C, 52.40; H, 5.21; N, 2.90.

Synthesis Example 32

Preparation of Me[Fc(CH.SUB.2.).SUB.5.]Si(4-Ph-2-MeC.SUB.9.H.SUB.4.)(NtBu)ZrCl.SUB.2 .

[0225] MeHSi(4-Ph-2-MeC.sub.9H.sub.4)(NtBu)ZrCl.sub.2 (0.96 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH.sub.2).sub.3CH═CH.sub.2 (0.559 g, 2.2 mmol)(note: Fc=CpFe(C.sub.5H.sub.4)) and B(C.sub.6F.sub.5).sub.3 (0.051 g, 0.1 mmol, usage of 5%) were added into the mixture, heated to 50° C. and reacted for 24 h. All the volatile components were removed by vacuuming at room temperature, and the remaining solid was washed with a small amount (approximately 1.5 mL each time) n-hexane for 2 to 4 times. Vacuum drying for 6 hours. A dark red solid Me[Fc(CH.sub.2).sub.5]Si(4-Ph-2-MeC.sub.9H.sub.4)(NtBu)ZrCl.sub.2 1.21 g (82.1%) was obtained.

[0226] The composition was C.sub.36H.sub.44Cl.sub.2FeNSiZr(Mr=736.81): theoretical value: C, 58.68; H, 6.02; N, 1.90; measured value: C, 58.66; H, 6.03; N, 1.92.

B. Preparation of Metallocene Catalysts

Preparation Example 1

[0227] 2 g of silica gel calcined at 600° C. was weighed, and 10 mL of 10% MAO toluene (weight percentage) was added into the silica gel, and heated to 80° C. After uniformly stirring, a toluene solution of the metallocene compound shown in formula 1 was added into the mixture, the Al/Zr ratio was controlled to be 200:1, and the reaction was carried out overnight. The solid was collected by filtration and washed with toluene solvent until the washed solvent was colorless, and the solid was dried under vacuum for 24 hours to obtain a solid powder, which was stored in a glove box for later use (this reaction operation method was used unless otherwise specified). Through the measurement and calculation of the feed amount and the metal content of the washing liquid, the catalyst SC-1 with a determined metal content could be obtained, and the zirconium content was 0.268% (29.4 μmol/g).

##STR00003##

Preparation Example 2

[0228] 2 g of silica gel calcined at 600° C. was weighed, 10 mL 10% MAO in toluene (weight percentage) and pure toluene solvent were added into the mixture, heated to 80° C., stirred for 24 h and then filtered. The solid was collected and washed with toluene solvent for 3 times. The solid was under vacuum drying for 24 h, and MAO-silica gel was obtained as a solid powder.

[0229] A certain amount of MAO-silica gel was weighed, toluene solvent was added to form a suspension. A toluene solution of zirconocene compound was added into the suspension under uniform stirring, and reacted overnight. The solid was collected by filtration and washed with toluene solvent until the washed solvent was colorless. The solid was vacuum dried for 24 hours to obtain a solid powder, which was stored in a glove box for later use. After the feed amount and the zirconium content of the washing liquid were measured and calculated, a catalyst with a certain zirconium content can be obtained.

[0230] The zirconocene compound of formula 1 was selected, with controlling the Al/Zr ratio to be 50:1, 100:1, and 150:1 to prepare catalysts SC-2A (zirconium content 0.846%, 100.2 μmol/g), SC-2B (zirconium content 0.430%, 47.2 μmol/g), SC-2C (zirconium content 0.282%, 32.2 μmol/g).

Preparation Example 3

[0231] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 2 was used and the Al/Zr ratio was controlled to be 193:1, 227:1, 340:1, to obtain catalysts SC-3A (zirconium content 0.40%, 28.4 μmol/g), SC-3B (zirconium content 0.30%, 25.0 μmol/g), SC-3C (zirconium content 0.20%, 16.7 μmol/g) respectively.

##STR00004##

Preparation Example 4

[0232] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 1 was used and the Al/Zr ratio was controlled to be 193:1, 194:1, 195:1, to obtain catalysts SC-4A (zirconium content 0.40%, 28.4 μmol/g), SC-4B (zirconium content 0.40%, 28.5 μmol/g), SC-4C (zirconium content 0.40%, 28.7 μmol/g) respectively.

Preparation Example 5

[0233] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 3 was used and the Al/Zr ratio was controlled to be 50:1, 100:1, 200:1, to obtain catalysts SC-5A (zirconium content 0.854%, 106.3 μmol/g), SC-5B(zirconium content 0.441%, 49.2 μmol/g), SC-5C(zirconium content 0.277%, 30.8 μmol/g) respectively.

##STR00005##

Preparation Example 6

[0234] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 4 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-6 (zirconium content 0.453%, 51.2 μmol/g).

##STR00006##

Preparation Example 7

[0235] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 5 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-7 (zirconium content 0.441%, 48.7 μmol/g).

##STR00007##

Preparation Example 8

[0236] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 6 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-8 (zirconium content 0.437%, 50.7 μmol/g).

##STR00008##

Preparation Example 9

[0237] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 7 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-9 (zirconium content 0.463%, 52.4 μmol/g).

##STR00009##

Preparation Example 10

[0238] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 8 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-10 (zirconium content 0.425%, 47.1 μmol/g).

##STR00010##

Preparation Example 11

[0239] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 9 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-11 (zirconium content 0.439%, 48.3 μmol/g).

##STR00011##

Preparation Example 12

[0240] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 10 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-12 (zirconium content 0.482%, 52.1 μmol/g).

##STR00012##

Preparation Example 13

[0241] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 11 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-13 (zirconium content 0.501%, 54.3 μmol/g).

##STR00013##

Preparation Example 14

[0242] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 12 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-14 (zirconium content 0.410%, 44.6 μmol/g).

##STR00014##

Preparation Example 15

[0243] 2 g of silica gel calcined at 600° C. was weighed, 10 mL of 10% (weight percentage) MAO in toluene was added into it, 0.30 g of tetrakis (pentafluorophenyl) borate dioctadecyl methyl ammonium salt was added into the mixture. and then 10 mL of toluene was added into the mixture, and heated to 80° C., stirred for 24 h. The resulting mixture was filtered, and the solid was collected and washed with toluene solvent for 3 times. The solid was vacuum dried for 24 h to obtain 3.1 g of solid powdered carrier silica gel.

[0244] 2 g of the treated carrier silica gel was weighed and 20 mL of toluene solvent was added into the carrier silica gel to form a suspension. 5 mL of toluene solution prepared by adding 100 mg of the zirconocene compound shown in Formula 12 was added into the suspension under uniformly stirring, and stirred at room temperature overnight. The solid was collected by filtration and washed with toluene solvent until the washed solvent was colorless. The solid was vacuum dried for 24 hours to obtain a solid catalyst powder (SC-15) with a Zr content of 0.390% by mass (42.39 μmol/g), which was stored in a glove box for later use.

Preparation Example 16

[0245] The only difference from Preparation Example 15 is that tris(pentafluorophenyl)borane of the same quality was used to replace tetrakis(pentafluorophenyl)borate dioctadecylmethylammonium salt and other conditions remained unchanged to obtain a solid catalyst 3.2 g, which has a tested zirconium content of 0.45% by mass.

Preparation Example 17

[0246] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 13 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-16 (zirconium content 0.406%, 43.7 μmol/g).

##STR00015##

Preparation Example 18

[0247] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 14 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-17 (zirconium content 0.415%, 45.9 μmol/g).

##STR00016##

Preparation Example 19

[0248] Preparation steps were the same as those in Preparation Example 2. The metallocene compound as shown in formula 15 was used and the Al/Zr ratio was controlled to be 100:1, to obtain a catalyst SC-18 (zirconium content 0.371%, 40.2 μmol/g).

##STR00017##

Preparation Example 20

[0249] Some of the metallocene compounds in Synthesis Examples 2-18 were taken to prepare catalysts for olefin polymerization. The preparation process was as follows:

[0250] 2 g of silica gel calcined at 600° C. was weighed, 10 mL 10% (weight percentage) MAO in toluene and pure toluene solvent 40-100 mL was added in it, heated to 80° C., and stirred for 24 h. The resulting mixture was filtered, and the solid was collected and washed with toluene solvent for three times. Next, the solid was dried under vacuum for 24 hours to obtain a solid powder of MAO-silica gel.

[0251] A certain amount of MAO-silica gel was weighed, toluene solvent was added into it to form a suspension. A part of the toluene solution of the zirconocene compound of the examples was added into the suspension under uniformly stirring, and reacted overnight. The solid was collected by filtration and washed with toluene solvent until the washed solvent was colorless, and the solid was vacuum dried for 24 hours to obtain a solid powder, which was stored in a glove box for later use. After the feed amount and the zirconium content of the washing liquid were measured and calculated, a catalyst with a certain zirconium content could be obtained.

[0252] Among them:

[0253] Al/Zr ratio was controlled to be 200:1 and zirconocene compound rac-MS-1b was taken, to obtain a catalyst rac-MS-1b-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0254] Al/Zr ratio was controlled to be 50:1 and zirconocene compound rac-MS-1j was taken, to obtain a catalyst rac-MS-1j-C, wherein zirconium content was 0.846% (100.2 μmol/g).

[0255] Al/Zr ratio was controlled to be 100:1 and zirconocene compound rac-MS-3a was taken, to obtain a catalyst rac-MS-3a-C, wherein zirconium content was 0.430% (47.2 μmol/g).

[0256] Al/Zr ratio was controlled to be 200:1 and zirconocene compound rac-MS-3b was taken, to obtain a catalyst rac-MS-3b-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0257] Al/Zr ratio was controlled to be 200:1 and zirconocene compound rac-MS-4a was taken, to obtain a catalyst rac-MS-4a-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0258] Al/Zr ratio was controlled to be 200:1 and zirconocene compound rac-MS-4b was taken, to obtain a catalyst rac-MS-4b-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Preparation Example 21

[0259] The metallocene compounds prepared in Synthesis Examples 19-32 were used to prepare the catalyst for olefin polymerization. The preparation process was as follows:

[0260] 2 g of silica gel calcined at 600° C. was weighed, 10 mL 10% (weight percentage) MAO in toluene and pure toluene solvent 40-100 mL was added into it, heated to 80° C. and stirred for 24 h. The resulting mixture was filtered, and the solid was collected and washed with toluene solvent three times. Next, the solid was dried under vacuum for 24 hours to obtain a solid powder of MAO-silica gel.

[0261] A certain amount of MAO-silica gel was weighed, toluene solvent was added to form a suspension. A part of the toluene solution of the zirconocene compound of the examples was added into the mixture under uniformly stirring, and react overnight. The solid was collected by filtration and washed with toluene solvent until the washed solvent was colorless, and the solid was vacuum dried for 24 hours to obtain a solid powder, which was stored in a glove box for later use. After the feed amount and the zirconium content of the washing liquid were measured and calculated, a catalyst with a certain zirconium content could be obtained.

[0262] Among them:

[0263] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[(PhMeN(CH.sub.2).sub.5)]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3c-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0264] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[PhMeN(CH.sub.2).sub.5]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrC.sub.2 was taken, to obtain a catalyst rac-MS-3d-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0265] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[PhMeN(CH.sub.2).sub.12]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3e-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0266] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[PhMeN(CH.sub.2).sub.15]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3f-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0267] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[p-ClC.sub.6H.sub.4MeN(CH.sub.2).sub.5]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3 g-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0268] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[p-MeOC.sub.6H.sub.4MeN(CH.sub.2).sub.5]Si(2-Me-7-PhC.sub.9H.sub.4) ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3h-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0269] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH.sub.2).sub.5]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3i, wherein zirconium content was 0.268% (29.4 μmol/g).

[0270] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me(Fc(CH.sub.2).sub.5)Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3j, wherein zirconium content was 0.268% (29.4 μmol/g).

[0271] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH.sub.2).sub.12]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3k-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0272] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH.sub.2).sub.15]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3l, wherein zirconium content was 0.268% (29.4 μmol/g).

[0273] Al/Zr ratio was controlled to be 200:1 and zirconocene compound MenBuSi(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3m-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0274] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[n-CH.sub.3(CH.sub.2);]Si(2-Me-7-PhC.sub.9H.sub.4).sub.2ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3n-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0275] Al/Zr ratio was controlled to be 200:1 and compound MeHSi(4-Ph-2-MeC.sub.9H.sub.4)(NtBu)ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3o-C, wherein zirconium content was 0.268% (29.4 μmol/g).

[0276] Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH.sub.2).sub.5]Si(4-Ph-2-MeC.sub.9H.sub.4)(NtBu)ZrCl.sub.2 was taken, to obtain a catalyst rac-MS-3p-C, wherein zirconium content was 0.268% (29.4 μmol/g).

C. Catalytic Reaction

Example 1

[0277] A 300 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0278] The pressurized catalyst adding device was dried and transferred into a glove box, added a measured amount of catalyst, and added a small amount of solvent to mix well. The device was took out from the glove box, and attached to the autoclave device to start the polymerization experiment.

[0279] The polymerization experiment conditions are as follows: setting a certain temperature, pressure and reaction time. Taking into account the industrial production and application, the polymerization experiments that have been completed gave priority to the choice of co-catalysts, that is, avoiding or minimizing the use of expensive MAO, and switching to using cheaper alkyl aluminum reagents. (If there was no special instructions below, this reaction method was used.)

[0280] 200 mg of SC-1 catalyst was used, without using solvent, the reaction time was 30 minutes, the reaction temperature was 80° C., and 50 g of propylene was pressed into the device.

[0281] Finally, 23.5 g of polymer was obtained, and the calculated activity was 2.35×10.sup.6 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 2

[0282] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0283] 105 mg of SC-2A catalyst and 8 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 500:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the pressure of propylene >3.9 MPa.

[0284] Finally, 92 g of polymer was obtained, and the calculated polymerization activity was 4.00×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 131324, the Mw was 325745, and the PDI value was 2.48, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.4%. The melting point test value was 151.33° C. (Note: PP analysis was selective.)

Example 3

[0285] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0286] 105 mg of SC-2B catalyst and 3.2 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the pressure of propylene >3.9 MPa.

[0287] Finally, 64 g of polymer was obtained, and the calculated polymerization activity was 2.78×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 4

[0288] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0289] 106 mg of SC-2C catalyst, triisobutyl aluminum 3.2 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the pressure of propylene >3.9 MPa.

[0290] Finally, 57 g of polymer was obtained, and the calculated polymerization activity was 2.45×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 5

[0291] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0292] 105 mg of SC-3A catalyst and 8 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 500:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the pressure of propylene >3.9 MPa.

[0293] Finally, 80 g of polymer was obtained, and the calculated polymerization activity was 3.48×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 133064, the Mw was 313745, and the PDI value was 2.36, all of them were measured by the high temperature GPC; and the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.3%. The melting point test value was 149.43° C.

Example 6

[0294] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0295] 105 mg of SC-3B catalyst and 3.2 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the pressure of propylene >3.9 MPa.

[0296] Finally, 52 g of polymer was obtained, and the calculated polymerization activity was 2.26×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 7

[0297] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0298] SC-3C catalyst 106 mg and triisobutyl aluminum 3.2 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the pressure of propylene >3.9 MPa.

[0299] Finally, 43 g of polymer was obtained, and the calculated polymerization activity was 1.85×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 8

[0300] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0301] 98 mg of SC-4A catalyst and 15 mL of triisobutyl aluminum (concentration of 150 mol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 528.7 g.

[0302] Finally, 450 g of polymer was obtained, and the calculated polymerization activity was 1.098×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. Mn was 162913, Mw was 377577, and PDI value was 2.317, all of them were measured by the high temperature GPC; the isotacticity measured by high temperature .sup.13C NMR spectrum was [mmmm] 99.6%. The melting point test value was 151.4° C.

Example 9

[0303] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0304] SC-4A catalyst 60 mg and triisobutyl aluminum 15 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 896:1 amount) were used, the reaction time was 330 minutes, the reaction temperature was 75° C., and the amount of propylene was 518 g.

[0305] Finally, 860 g of polymer was obtained, and the calculated polymerization activity was 1.772×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 104205, the Mw was 226218, and the PDI value was 2.17, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 152.2/161.4° C.

Example 10

[0306] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0307] SC-4A catalyst 60 mg and triethylaluminum 3 mL (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene 538 g, and the amount of hydrogen was 0.02 g.

[0308] Finally, 80 g of polymer was obtained, and the calculated polymerization activity was 3.186×10.sup.7 g(PP).Math.mol(Zr).Math.h.sup.−1.

Example 11

[0309] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0310] 35 mg of SC-4A catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1707:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0311] Finally, 35 g of polymer was obtained, and the calculated polymerization activity was 2.389×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 12

[0312] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0313] SC-4A catalyst 65 mg and triisobutyl aluminum 20 mL (concentration of 150 μmol/mL, and aluminum zirconium ratio of about 1792:1 amount) were used, the reaction time was 270 minutes, the reaction temperature was 75° C., the amount of propylene was 659 g, the amount of hydrogen was 0.026 g.

[0314] Finally, 600 g of polymer was obtained, and the calculated polymerization activity was 2.206×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 80551, the Mw was 188015, and the PDI value was 2.33, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.7%. The melting point test value was 151.83/152.2° C.

Example 13

[0315] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0316] 40 mg SC-4A catalyst and triisobutyl aluminum 20 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1707:1 volume) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 628.6 g, and the amount of hydrogen was 1.365 g.

[0317] Finally, 270 g of polymer was obtained, and the calculated polymerization activity was 1.613×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 14

[0318] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0319] SC-4A catalyst 30 mg, triisobutyl aluminum 20 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 2389:1 volume) were used, the reaction time was 360 minutes, the reaction temperature was 75° C., the amount of propylene was 658.8 g, and the amount of hydrogen was 0.052 g.

[0320] Finally, 390 g of polymer was obtained, and the calculated polymerization activity was 3.106×10.sup.8 g(PP).Math.mol(Zr).Math.h.sup.−1. Mn was 47736, Mw was 146937, and PDI value was 3.08, all of them were measured by the high temperature GPC.

Example 15

[0321] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0322] SC-4A catalyst 30 mg and triisobutyl aluminum 20 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 2389:1 volume) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene is 357.2 g, and the amount of hydrogen was 0.06 g.

[0323] Finally, 205 g of polymer was obtained, and the calculated polymerization activity was 1.633×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The melting point test value was 154.03° C.

Example 16

[0324] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0325] SC-4A catalyst 30 mg, triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1195.1) were used, the reaction time was 420 minutes, the reaction temperature was 75° C., the amount of propylene was 682 g, and the amount of hydrogen was 0.06 g.

[0326] Finally, 540 g of polymer was obtained, and the calculated polymerization activity was 4.301×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 17

[0327] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0328] SC-4A catalyst 20 mg and triisobutyl aluminum 3.5 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 627:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 657 g, and the amount of hydrogen was 0.06 g.

[0329] Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 1.195×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 18

[0330] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0331] SC-4A catalyst 20 mg and triisobutyl aluminum 7 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1254:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 651 g, and the amount of hydrogen was 0.06 g.

[0332] Finally, 45 g of polymer was obtained, and the calculated polymerization activity was 5.376×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 19

[0333] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0334] SC-4A catalyst 20 mg, triisobutyl aluminum 10 mL (concentration of 150 μl mol/mL, aluminum-zirconium ratio of about 1792:1 amount), the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 654 g, the amount of hydrogen was 0.06 g.

[0335] Finally, 82 g of polymer was obtained, and the calculated polymerization activity was 9.797×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 20

[0336] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0337] SC-4A catalyst 20 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1792:1 amount) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 652 g, and the amount of hydrogen was 0.06 g.

[0338] Finally, 92 g of polymer was obtained, and the calculated polymerization activity was 1.099×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 21

[0339] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0340] SC-4A catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1195:1 volume) were used, the reaction time was 420 minutes, the reaction temperature was 75° C., the amount of propylene was 670 g, and the amount of hydrogen was 0.06 g.

[0341] Finally, 530 g of polymer was obtained, and the calculated polymerization activity was 4.221×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 22

[0342] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0343] SC-4B catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, the reaction time was 480 minutes, the reaction temperature was 75° C., the amount of propylene was 684 g, and the amount of hydrogen was 0.06 g.

[0344] Finally, 610 g of polymer was obtained, and the calculated polymerization activity was 4.859×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 23

[0345] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0346] SC-4B catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, the reaction time was 240 minutes, reaction temperature was 75° C., the amount of propylene was 687.5 g, and the amount of hydrogen was 0.06 g.

[0347] Finally, 533 g of polymer was obtained, and the calculated polymerization activity was 4.245×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The melting point test value was 155.46° C.

Example 24

[0348] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0349] SC-4B catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., the amount of propylene was 688.6 g, and the amount of hydrogen was 0.06 g.

[0350] Finally, 405 g of polymer was obtained, and the calculated polymerization activity was 3.226×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 25

[0351] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0352] SC-4C catalyst 30 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 680 g, and the amount of hydrogen was 0.06 g.

[0353] Finally, 530 g of polymer was obtained, and the calculated polymerization activity was 4.221×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 26

[0354] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0355] SC-4C catalyst 20 mg and triisobutyl aluminum 10 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 1792:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 681 g, and the amount of hydrogen was 0.06 g.

[0356] Finally, 145 g of polymer was obtained, and the calculated polymerization activity was 1.732×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 27

[0357] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0358] 98 mg of SC-5A catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum to zirconium ratio of about 549:1 amount) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene amount was 523 g.

[0359] Finally, 461 g of polymer was obtained, and the calculated polymerization activity was 1.106×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h. The Mn was 174912, the Mw was 366583, and the PDI value was 2.09, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 153.1° C.

Example 28

[0360] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0361] SC-5B catalyst 60 mg and triisobutyl aluminum 15 mL (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 896:1 amount) were used, the reaction time was 330 minutes, the reaction temperature was 75° C., and the amount of propylene was 521 g.

[0362] Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.788×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 115708, the Mw was 236654, and the PDI value was 2.045, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.1%. The melting point test value was 154.9° C.

Example 29

[0363] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0364] SC-5C catalyst 60 mg and triethylaluminum 3 mL (concentration 100 μmol/mL, aluminum-zirconium ratio of about 1195:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 534 g, and the amount of hydrogen was 0.02 g.

[0365] Finally, 91 g of polymer was obtained, and the calculated polymerization activity was 1.641×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 30

[0366] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0367] 98 mg of SC-6 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 541 g.

[0368] Finally, 424 g of polymer was obtained, and the calculated polymerization activity was 2.112×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. Mn was 168742, Mw was 368213, and PDI value was 2.18, all of them were measured by the high temperature GPC; the isotacticity measured by high temperature .sup.13C NMR spectrum was [mmmm] 98.9%. The melting point test value was 155.4° C.

Example 31

[0369] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0370] 100 mg of SC-7 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 mol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 539 g.

[0371] Finally, 447 g of polymer was obtained, and the calculated polymerization activity was 2.294×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 19,863, the Mw was 398423, and the PDI value was 2.01, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.2%. The melting point test value was 157.1° C.

Example 32

[0372] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0373] 100 mg of SC-8 catalyst, and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene amount was 534 g.

[0374] Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.223×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 215821, the Mw was 439429, and the PDI value was 2.036, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.4%. The melting point test value was 159.1° C.

Example 33

[0375] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0376] 100 mg of SC-9 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 544 g.

[0377] Finally, 472 g of polymer was obtained, and the calculated polymerization activity was 2.252×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 175941, the Mw was 419745, and the PDI value was 2.386, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.5%. The melting point test value was 161.4° C.

Example 34

[0378] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0379] 100 mg of SC-10 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 521 g.

[0380] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.489×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 155967, the Mw was 430741, and the PDI value was 2.762, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 97.2%. The melting point test value was 147.9° C.

Example 35

[0381] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0382] 100 mg of SC-11 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 521 g.

[0383] Finally, 471 g of polymer was obtained, and the calculated polymerization activity was 2.437×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 152134, the Mw was 416572, and the PDI value was 2.738, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature 13C NMR spectrum was [mmmm] 97.5%. The melting point test value was 148.1° C.

Example 36

[0384] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0385] 100 mg of SC-12 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 529 g.

[0386] Finally, 487 g of polymer was obtained, and the calculated polymerization activity was 2.336×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 142879, the Mw was 396654, and the PDI value was 2.776, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 96.6%. The melting point test value was 144.7° C.

Example 37

[0387] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0388] 100 mg of SC-13 catalyst, and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 542 g.

[0389] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.159×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 162678, the Mw was 396789, and the PDI value was 2.439, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 97.6%. The melting point test value was 152.9° C.

Example 38

[0390] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0391] 100 mg of SC-14 catalyst, and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 582 g.

[0392] Finally, 459 g of polymer was obtained, and the calculated polymerization activity was 2.573×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. Mn was 182668, Mw was 406769, and PDI value was 2.226, all of them were measured by the high temperature GPC; the isotacticity measured by high temperature .sup.13C NMR spectrum was [mmmm] 95.6%. The melting point test value was 147.9° C.

Example 39

[0393] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0394] 100 mg of SC-15 catalyst, and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 552 g.

[0395] Finally, 485 g of polymer was obtained. The PDI value measured by high temperature GPC was 2.028; the isotacticity measured by high temperature .sup.13C NMR spectrum was [mmmm] 96.3%. The melting point test value was 148.5° C.

Example 40

[0396] The evaluation conditions were the same as in Example 39, and the catalyst prepared in Example 16 was used. 560 g of propylene was used and 300 g of polypropylene powder was obtained. The PDI measured by GPC was 2.678, and the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 92.6%. The melting point test value was 145.1° C.

Example 41

[0397] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0398] 100 mg of SC-16 catalyst and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 582 g.

[0399] Finally, 418 g of polymer was obtained, and the calculated polymerization activity was 2.434×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 172761, the Mw was 435432, and the PDI value was 2.520, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 96.7%. The melting point test value was 148.8° C.

Example 42

[0400] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0401] 100 mg of SC-17 catalyst, and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 582 g.

[0402] Finally, 401 g of polymer was obtained, and the calculated polymerization activity was 2.248×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 123758, the Mw was 467327, and the PDI value was 3.776, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 92.4%. The tested melting point was 140.2° C.

Example 43

[0403] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0404] 100 mg of SC-18 catalyst, and 15 mL of triisobutyl aluminum (concentration of 150 μmol/mL) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 582 g.

[0405] Finally, 491 g of polymer was obtained, and the calculated polymerization activity was 2.752×10.sup.7 g(PP) mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 186469, the Mw was 404219, and the PDI value was 2.168, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 97.2%. The melting point test value was 148.7° C.

Example 44

[0406] A 300 mL autoclave was used for the polymerization reaction (300 mL reactor was used in the following examples unless otherwise specified), vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0407] The pressurized catalyst adding device was dried and transferred into a glove box, added a measured amount of catalyst, and added a small amount of solvent to mix well. The device was took out from the glove box, and attached to the autoclave device to start the polymerization experiment.

[0408] The polymerization experiment conditions are as follows: setting a certain temperature, pressure and reaction time. Taking into account the industrial production and application, the polymerization experiments that have been completed gave priority to the choice of co-catalysts, that is, avoiding or minimizing the use of expensive MAO, and switching to using cheaper alkyl aluminum reagents.

[0409] 50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum/zirconium ratio of about 200) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure in the autoclave was 1 MPa.

[0410] Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 6.8×10.sup.6 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 45

[0411] The polymerization conditions were basically the same as in Example 44, except that 50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum/zirconium ratio of about 200), the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 2 MPa.

[0412] Finally, 16 g of polymer was obtained, and the calculated polymerization activity was 1.08×10.sup.7 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 46

[0413] The polymerization conditions were basically the same as those in Example 44, except that 150 mg of rac-MS-1b-C catalyst and 0.2 mL of MAO (10% by mass in Tol, aluminum/zirconium ratio of about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 1 MPa.

[0414] Finally, 35 g of polymer was obtained, and the calculated polymerization activity was 6.99′10.sup.6 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 47

[0415] The polymerization conditions were basically the same as those in Example 44, except that: 113 mg of rac-MS-1j-C catalyst and 15 mL of triisobutyl aluminum solution (concentration of 150 μmol/mL, aluminum/zirconium ratio of about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 1 MPa.

[0416] Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 0.88×10.sup.6 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 48

[0417] The polymerization conditions were basically the same as those in Example 44, except that: 150 mg of rac-MS-3a-C catalyst and 6.3 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum/zirconium ratio of about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 1 MPa.

[0418] Finally, 21 g of polymer was obtained, and the calculated polymerization activity was 4.45×10.sup.6 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 49

[0419] The polymerization conditions were basically the same as those in Example 44, except that 150 mg of rac-MS-3b-C catalyst and 1.75 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 1 MPa.

[0420] Finally, 36 g of polymer was obtained, and the calculated polymerization activity was 2.74×10.sup.7 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 50

[0421] The polymerization conditions were basically the same as those in Example 44, except that 150 mg of rac-MS-4a-C catalyst and 6.3 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum/zirconium ratio of about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 1 MPa.

[0422] Finally, 54 g of polymer was obtained, and the calculated polymerization activity was 1.22×10.sup.7 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 51

[0423] The polymerization conditions were basically the same as those in Example 44, except that 150 mg of rac-MS-4b-C catalyst and 3.75 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50° C., and the ethylene pressure was 2 MPa.

[0424] Finally, 62 g of polymer was obtained, and the calculated polymerization activity was 1.41×10.sup.7 g(PE).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 52

[0425] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0426] 112 mg of rac-MS-1b-C catalyst and 8 mL of triisobutyl aluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 500:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the propylene pressure>3.9 MPa.

[0427] Finally, 91 g of the polymer was obtained, and the calculated polymerization activity was 9.20×10.sup.6 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 133945, the Mw was 342375, and the PDI value was 2.57, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.3%. The melting point test value was 157.63° C.

Example 53

[0428] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0429] 101 mg of rac-MS-1j-C catalyst and 3.2 mL of triisobutylaluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., and the propylene pressure >3.9 MPa.

[0430] Finally, 132 g of polymer was obtained, and the calculated polymerization activity was 4.33×10.sup.6 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 127361, the Mw was 36.431, and the PDI value was 2.83, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 98.6%. The melting point test value was 152.3° C.

Example 54

[0431] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0432] 104 mg of rac-MS-1b-C catalyst and 15 mL of triisobutylaluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., and the amount of propylene was 528.7 g.

[0433] Finally, 412 g of polymer was obtained, and the calculated polymerization activity was 3.37×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 173453, the Mw was 394257, and the PDI value was 2.273, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 99.1%. The melting point test value was 154.4° C.

Example 55

[0434] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0435] 104 mg of rac-MS-1b-C catalyst and 15 mL of triethylaluminum (concentration of 150 μmol/mL, aluminum-zirconium ratio of about 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75° C., the amount of propylene was 538 g, and the amount of hydrogen was 0.02 g.

[0436] Finally, 478 g of polymer was obtained, and the calculated polymerization activity was 1.54×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 135427, the Mw was 397892, and the PDI value was 2.938, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 153.2° C.

Example 56

[0437] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0438] 35 mg of rac-MS-1j-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1707:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0439] Finally, 135 g of polymer was obtained, and the calculated polymerization activity was 4.37×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1. The Mn was 82451, the Mw was 213509, and the PDI value was 2.59, all of them were measured by the high temperature GPC; the isotacticity measured by the high temperature .sup.13C NMR spectrum was [mmmm] 96.7%. The melting point test value was 147.83/150.2° C.

Example 57

[0440] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0441] 35 mg of rac-MS-3c-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0442] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 1.52×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 58

[0443] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0444] 35 mg of rac-MS-3d-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0445] Finally, 455 g of polymer was obtained, and the calculated polymerization activity was 1.47×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 59

[0446] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0447] 35 mg of rac-MS-3e-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0448] Finally, 492 g of polymer was obtained, and the calculated polymerization activity was 1.59×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 60

[0449] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0450] 35 mg of rac-MS-3f-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0451] Finally, 421 g of polymer was obtained, and the calculated polymerization activity was 1.36×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 61

[0452] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0453] 35 mg of rac-MS-3 g-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1), the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene is 512 g, and the amount of hydrogen was 0.02 g.

[0454] Finally, 387 g of polymer was obtained, and the calculated polymerization activity was 1.25×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 62

[0455] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0456] 35 mg of rac-MS-3h-C catalyst, 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, the ratio of aluminum to zirconium was about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene is 512 g, and the amount of hydrogen was 0.02 g.

[0457] Finally, 418 g of polymer was obtained, and the calculated polymerization activity was 1.35×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 63

[0458] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0459] 35 mg of rac-MS-3i-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0460] Finally, 441 g of polymer was obtained, and the calculated polymerization activity was 1.43×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 64

[0461] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0462] 35 mg of rac-MS-3j-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0463] Finally, 427 g of polymer was obtained, and the calculated polymerization activity was 1.38×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 65

[0464] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0465] 35 mg of rac-MS-3k-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0466] Finally, 434 g of polymer was obtained, and the calculated polymerization activity was 1.41×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 66

[0467] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0468] 35 mg of rac-MS-3l-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0469] Finally, 395 g of polymer was obtained, and the calculated polymerization activity was 1.27×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Example 67

[0470] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0471] 35 mg of rac-MS-3p-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0472] Finally, 352 g of polymer was obtained, and the calculated polymerization activity was 1.14′10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Comparative Example 1

[0473] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0474] 35 mg of rac-MS-3m-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1), the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0475] Finally, 425 g of polymer was obtained, and the calculated polymerization activity was 1.38×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Comparative Example 2

[0476] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0477] 35 mg of rac-MS-3n-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0478] Finally, 420 g of polymer was obtained, and the calculated polymerization activity was 1.36×10.sup.8 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

Comparative Example 3

[0479] A 2000 mL autoclave was selected, vacuumed in an oil bath at 100° C., and replaced with nitrogen for 3 times before use.

[0480] 35 mg of rac-MS-3o-C catalyst and 2.5 mL of triethylaluminum (concentration of 100 μmol/mL, aluminum-zirconium ratio of about 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75° C., the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0481] Finally, 268 g of polymer was obtained, and the calculated polymerization activity was 8.68×10.sup.7 g(PP).Math.mol.sup.−1(Zr).Math.h.sup.−1.

[0482] For easy comparison and analysis, the above experimental data are summarized in the following tables.

TABLE-US-00001 TABLE 1 Polymerization product properties Catalyst Reaction Melting Al/Zr Al/Zr Metallocene compound Catalyst Isotacticity point Item Catalyst ratio ratio R.sup.I R.sup.II (Cp.sup.III).sub.n(E).sub.2−n Activity Mn Mw PDIvvalue (%) (° C.) Example SC-1 200:1 — Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 2.35 — — — — — 1 Example SC-2A  50:1  500:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 40 131324 325745 2.48 99.4 151.33 2 Example SC-2B 100:1  200:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 27.8 — — — — — 3 Example SC-2C 150:1  200:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 24.5 — — — — — 4 Example SC-3A 193:1  500:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 34.8 133064 313745 2.36 99.3 149.43 5 Example SC-3B 227:1  200:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 22.6 — — — — — 6 Example SC-3C 340:1  200:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 18.5 — — — — — 7 Example SC-4A 193:1  549:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 109.8 162913 377577 2.317 99.6 151.4 8 Example SC-4A 193:1  896:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 177.2 104205 226218 2.17 98.4 161.4 9 Example SC-4A 193:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 31.86 — — — — — 10 Example SC-4A 193:1 1707:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 23.89 — — — — — 11 Example SC-4A 193:1 1792:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 220.6 80551 188015 2.33 99.7 152.2 12 Example SC-4A 193:1 1707:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 161.3 — — — — — 13 Example SC-4A 193:1 2389:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 310.6 47736 146937 3.08 — — 14 Example SC-4A 193:1 2389:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 163.3 — — — — 154.03 15 Example SC-4A 193:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2-MeC.sub.9H.sub.4).sub.2 430.1 — — — — — 16

TABLE-US-00002 TABLE 2 Polymerization product properties Catalyst Reaction Melting Al/Zr Al/Zr Metallocene compound Catalyst PD Isotacticity point Item Catalyst ratio ratio R.sup.I R.sup.II (Cp.sup.III).sub.n(E).sub.2−n activity Mn Mw value (%) (° C.) Example SC-4A 193:1  627:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 11.95 — — — — — 17 MeC.sub.9H.sub.4).sub.2 Example SC-4A 193:1 1254:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 53.76 — — — — — 18 MeC.sub.9H.sub.4).sub.2 Example SC-4A 193:1 1792:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 97.97 — — — — — 19 MeC.sub.9H.sub.4).sub.2 Example SC-4A 193:1 1792:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 109.9 — — — — — 20 MeC.sub.9H.sub.4).sub.2 Example SC-4A 193:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 422.1 — — — — — 21 MeC.sub.9H.sub.4).sub.2 Example SC-4B 194:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 485.9 — — — — — 22 MeC.sub.9H.sub.4).sub.2 Example SC-4B 194:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 424.5 — — — — 155.46 23 MeC.sub.9H.sub.4).sub.2 Example SC-4B 194:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 322.6 — — — — — 24 MeC.sub.9H.sub.4).sub.2 Example SC-4C 195:1 1195:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 422.1 — — — — — 25 MeC.sub.9H.sub.4).sub.2 Example SC-4C 195:1 1792:1 Me PhMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 173.2 — — — — — 26 MeC.sub.9H.sub.4).sub.2 Example SC-5A  50:1  549:1 Me Me.sub.2NH.sub.2CH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 11.06 174912 366583 2.09 98.4 153.1 27 MeC.sub.9H.sub.4).sub.2 Example SC-5B 100:1  896:1 Me Me.sub.2NH.sub.2CH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 27.88 115708 236654 2.045 99.1 154.9 28 MeC.sub.9H.sub.4).sub.2 Example SC-5C 200:1 1195:1 Me Me.sub.2NH.sub.2CH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 16.41 — — — — — 29 MeC.sub.9H.sub.4).sub.2 Example SC-6 100:1  549:1 Me Me.sub.2NH.sub.2CH.sub.2C (4-Ph-2- 21.12 168742 368213 2.18 98.9 155.4 30 MeC.sub.9H.sub.4).sub.2 Example SC-7 100:1  549:1 Me (Me.sub.2NH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 22.94 198563 398423 2.01 99.2 157.1 31 MeC.sub.9H.sub.4).sub.2 Example SC-8 100:1  549:1 Me NH.sub.2Pr.sub.2NH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 22.23 215821 439429 2.036 99.4 159.1 32 MeC.sub.9H.sub.4).sub.2

TABLE-US-00003 TABLE 3 Polymerization product properties Catalyst Reaction Isotac- Melting Al/Zr Al/Zr Metallocene compound Catalyst PDI ticity point Item Catalyst ratio ratio R.sup.I R.sup.II (Cp.sup.III).sub.n(E).sub.2−n activity Mn Mw value (%) (° C.) Example SC-9 100:1 549:1 Me iPr.sub.2NH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 22.52 175941 419745 2.386 99.5 161.4 33 MeC.sub.9H.sub.4).sub.2 Example SC-10 100:1 549:1 Me iBuMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 24.89 155967 430741 2.762 97.2 147.9 34 MeC.sub.9H.sub.4).sub.2 Example SC-11 100:1 549:1 Me iBuEtNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 24.37 152134 416572 2.738 97.5 148.1 35 MeC.sub.9H.sub.4).sub.2 Example SC-12 100:1 549:1 Me iPrEtNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 23.36 142879 396654 2.776 96.6 144.7 36 MeC.sub.9H.sub.4).sub.2 Example SC-13 100:1 549:1 Me.sub.2NH.sub.2CH.sub.2C iBuMeNH.sub.2CH.sub.2CH.sub.2C (4-Ph-2- 21.59 162678 396789 2.439 97.6 152.9 37 MeC.sub.9H.sub.4).sub.2 Example SC-14 100:1 — Me FcCH.sub.2CH.sub.2 (4-Ph-2- 25.73 182668 406769 2.226 95.6 147.9 38 MeC.sub.9H.sub.4).sub.2 Example SC-15 — — Me FcCH.sub.2CH.sub.2 (4-Ph-2- — — — 2.028 96.3 148.5 39 MeC.sub.9H.sub.4).sub.2 Example Prep- — — Me FcCH.sub.2CH.sub.2 (4-Ph-2- — — — 2.678 92.6 145.1 40 aration MeC.sub.9H.sub.4).sub.2 Exam- ple 16 Example SC-16 100:1 — Me FcCH.sub.2CH.sub.2CH.sub.2 (4-Ph-2- 24.34 172761 435432 2.520 96.7 148.8 41 MeC.sub.9H.sub.4).sub.2 Example SC-17 100:1 — Me FcCH.sub.2 (4-Ph-2- 22.48 123758 467327 3.776 92.4 140.2 42 MeC.sub.9H.sub.4).sub.2 Example SC-18 100:1 — Me FcCH.sub.2CH.sub.2 (4-(4- 27.52 186469 404219 2.168 97.2 148.7 43 tBuC.sub.6H.sub.4)-2- MeC.sub.9H.sub.4).sub.2 Note: In Tables 1-3, the unit of catalyst activity in Examples 1-43 is 10.sup.6 g(PP) .Math. mol − 1(Zr) .Math. h.sup.−1. ″—″means there is no such data. According to the data in Tables 1-3: 1)When the substituents on the bridging atoms in the metallocene compound include amine-substituted C.sub.2-C.sub.4 groups or metallocene-substituted C.sub.1-C.sub.3 groups, the prepared catalyst has higher catalytic activity for the polymerization of propylene and obtained polymerization products with suitable molecular weights, PDI values, isotacticity and melting points. 2)By adjusting the types of substituents on the bridging atoms in the metallocene compound, polymerization products with different molecular weights and different melting points can be obtained. 3)The polymerization activity of the catalyst can be further optimized by adjusting the test conditions such as Al/Zr ratio of the catalyst and/or the Al/Zr ratio of the polymerization system, as illustrated by Examples 1-4, and Examples 8-11.

TABLE-US-00004 TABLE 4 Catalyst Reaction Metallocene Compound Catalyst Item Catalyst Al/Zr ratio Al/Zr ratio R.sup.I R.sup.II (Cp.sup.III).sub.n(E).sub.2−n activity Example rac-MS-1b-C 200:1 200:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-p-tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 6.8 44 Example rac-MS-1b-C 200:1 200:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-p-tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 10.8 45 Example rac-MS-1b-C 200:1 200:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-p-tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 6.99 46 Example rac-MS-1j-C  50:1 200:1 Me FcCH.sub.2CH.sub.2 (2-Me-7-p-tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 0.88 47 Example rac-MS-3a-C 100:1 200:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-PhC.sub.9H.sub.4).sub.2 4.45 48 Example rac-MS-3b-C 200:1 200:1 Me FcCH.sub.2CH.sub.2 (2-Me-7-PhC.sub.9H.sub.4).sub.2 27.4 49 Example rac-MS-4a-C 200:1 200:1 Me PhMeNCH.sub.2CH.sub.2 Flu.sub.2 12.2 50 Example rac-MS-4b-C 200:1 200:1 Me FcCH.sub.2CH.sub.2 Flu.sub.2 14.1 51 Note: The unit of catalyst activity in Examples 44-51 is 10.sup.6 g(PE) .Math. mol.sup.−1(Zr) .Math. h.sup.−1. According to the data in Table 4: 1)When the substituent on the bridging atom in the metallocene compound contains an amine-substituted C.sub.2 group or a metallocene-substituted C.sub.2 group, the prepared catalyst has higher catalytic activity for the polymerization of ethylene. 2)The polymerization activity of the catalyst can be further optimized by adjusting the test conditions such as Al/Zr ratio of the catalyst and/or the Al/Zr ratio of the polymerization system, as illustrated by Examples 44-45.

TABLE-US-00005 TABLE 5 Polymerization product property Catalyst Reaction Melting ratio ratio Metallocene compound Catalyst PDI Isotacticity point Item Catalyst Al/Zr Al/Zr R.sup.I R.sup.II (Cp.sup.III).sub.n(E).sub.2−n activity Mn Mw value (%) (° C.) Example rac-MS-1b- 200:1  500:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-p- 9.2 133945 342375 2.57 99.3 157.63 52 C tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 Example rac-MS-1j- 200:1  200:1 Me FcCH.sub.2CH.sub.2 (2-Me-7-p- 4.33 127361 36.431 2.83 98.6 152.3 53 C tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 Example rac-MS-1b- 200:1  549:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-p- 33.7 173453 394257 2.273 99.1 154.4 54 C tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 Example rac-MS-1b- 200:1  549:1 Me PhMeNCH.sub.2CH.sub.2 (2-Me-7-p- 154 135427 397892 2.938 98.4 153.2 55 C tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 Example rac-MS-1j- 200:1 1707:1 Me FcCH.sub.2CH.sub.2 (2-Me-7-p- 43.7 82451 213509 2.59 96.7 150.2 56 C tBuC.sub.6H.sub.4C.sub.9H.sub.4).sub.2 Note: In Table 5, the unit of catayst activity in Examples 52-58 is 10.sup.6 g(PP) .Math. mol.sup.−1(Zr) .Math. h.sup.−1. According to the data in Table 5: 1)When the substituent on the bridging atom in the metallocene compound contains an amine-substituted C.sub.2 group or a metallocene-substituted C.sub.2 group, the prepared catalyst has higher catalytic activity for the polymerization of propylene.. 2)The polymerization activity of the catalyst can be further optimized by adjusting the test conditions such as Al/Zr ratio of the catalyst and/or the Al/Zr ratio of the polymerization system, as illustrated by Examples 52, 54, and 56.

TABLE-US-00006 TABLE 6 Catalyst Reaction Metallocene Compound Catalyst Item Catalyst Al/Zr ratio Al/Zr ratio R.sup.I R.sup.II (Cp.sup.III).sub.n(E).sub.2−n activity Example 57 rac-MS-3c-C 200:1 1200:1 Me PhMeN(CH.sub.2).sub.5 (2-Me-7-PhC.sub.9H.sub.4).sub.2 152 Example 58 rac-MS-3d-C 200:1 1200:1 Me PhMeN(CH.sub.2).sub.8 (2-Me-7-PhC.sub.9H.sub.4).sub.2 147 Example 59 rac-MS-3e-C 200:1 1200:1 Me PhMeN(CH.sub.2).sub.12 (2-Me-7-PhC.sub.9H.sub.4).sub.2 159 Example 60 rac-MS-3f-C 200:1 1200:1 Me PhMeN(CH.sub.2).sub.15 (2-Me-7-PhC.sub.9H.sub.4).sub.2 136 Example 61 rac-MS-3g-C 200:1 1200:1 Me p-ClC.sub.6H.sub.4MeN(CH.sub.2).sub.5 (2-Me-7-PhC.sub.9H.sub.4).sub.2 125 Example 62 rac-MS-3h-C 200:1 1200:1 Me p-MeOC.sub.6H.sub.4MeN(CH.sub.2).sub.5 (2-Me-7-PhC.sub.9H.sub.4).sub.2 135 Example 63 rac-MS-3i-C 200:1 1200:1 Me Fc(CH.sub.2).sub.5 (2-Me-7-PhC.sub.9H.sub.4).sub.2 143 Example 64 rac-MS-3j-C 200:1 1200:1 Me Fc(CH.sub.2).sub.8 (2-Me-7-PhC.sub.9H.sub.4).sub.2 138 Example 65 rac-MS-3k-C 200:1 1200:1 Me Fc(CH.sub.2).sub.12 (2-Me-7-PhC.sub.9H.sub.4).sub.2 141 Example 66 rac-MS-3l-C 200:1 1200:1 Me Fc(CH.sub.2).sub.18 (2-Me-7-PhC.sub.9H.sub.4).sub.2 127 Example 67 rac-MS-3p-C 200:1 1200:1 Me Fc(CH.sub.2).sub.5 (4-Ph-2-MeC.sub.9H.sub.4)(NtBu) 114 Comparative rac-MS-3m-C 200:1 1200:1 Me nBu (2-Me-7-PhC.sub.9H.sub.4).sub.2 138 Example 1 Comparative rac-MS-3n-C 200:1 1200:1 Me n-CH.sub.3(CH.sub.2).sub.7 (2-Me-7-PhC.sub.9H.sub.4).sub.2 136 Example2 Example 67 rac-MS-3o-C 200:1 1200:1 Me H (4-Ph-2-MeC.sub.9H.sub.4)(NtBu) 86.8 Note: In Table 6, the unit of catalyst activity in Examples 57-67 is 10.sup.6 g(PP) .Math. mol.sup.−1(Zr) .Math. h.sup.−1. ″--″ means there is no such data.

[0483] According to the data in Table 6:

[0484] When the substituent on the bridging atom in the metallocene compound is a C.sub.5-C.sub.15 group substituted with an amine group or a C.sub.5-C.sub.15 group substituted with a metallocene group, the prepared catalyst has higher catalytic activity for the polymerization of propylene.

[0485] According to the data in Tables 1-6:

[0486] Compared with the substituent on the bridging atom in the metallocene compound that do not contain an amine-substituted group or a metallocene-substituted group, when the substituent on the bridging atom in the metallocene compound is the amine-substituted group or the metallocene-substituted group, the prepared catalyst has higher catalytic activity for the polymerization of propylene.