METALLOCENE COMPOUND, AND PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

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.  RIRIIZ(CpIII)n(E)2-nMLIVLV   (I)

The present application claims the priorities of the following patent applications filed on Oct. 30, 2019:

1. Chinese patent application CN201911047955.1, entitled “Transition metal catalyst with unsymmetrically bridged two indenyl groups, preparation method and use thereof”; and

the entirety of which is incorporated herein by reference.

FIELD OF TECHNOLOGY

The present disclosure is directed to a metallocene compound, preparation method and application thereof, and in particular to a metallocene catalyst containing the metallocene compound, preparation method and use of the catalyst. Specifically, the present disclosure is related to the technical field of metallocene catalysts.

BACKGROUND

Metallocene polypropylene (mPP) has good utility in fibers, injection molding and films, and thus the market demand thereof increases in recent years. These resin articles have high requirements on the stereoregular structure of polypropylene, and while the structure of polypropylene is adjusted and controlled by the structure of the catalyst.

Metallocene polypropylene with high isotactic structure is an important resin. Such metallocene polypropylene is synthesized by controlling the growth of the propylene chain through the stereo enantiomorphic site of the catalyst. The catalyst capable of controlling chain extension reaction through the stereo enantiomorphic site is required to have a C2 axis or a lower C1 axis symmetry (Chem. Rev. 2000, 100, 1223). The compounds of Group IV metals such as titanium, zirconium, or hafnium, and bridged diindene ring with racemic structure or derivatives thereof are with this characteristic. In the 1980s, Brintzinger team synthesized an ethyl diindene ligand with a racemic structure and the later ethyl bis(tetrahydroindene) ligand with a racemic structure (J. Organomet. Chem. 1982, 232, 233; 1985, 288, 63). The synthesized titanium and zirconium compounds catalyze propylene to form polypropylene with high isotactic structure under the action of a methylaluminoxane (MAO) additive, whereas the catalyst with meso structure cannot catalyze propylene to produce polypropylene with high isotacticity. The activity of these racemic catalysts, and the molecular weight and the isotacticity of the products are very sensitive to temperatures. In the range of from −20° C. to 60° C., the difference between the highest activity (84.43 kg PP/g Zr·h) and the lowest activity (0.88 kg PP)/g Zr·h) is nearly two orders of magnitude, the difference between the highest average molecular weight (300,000 Dalton) and the lowest one (12,000 Dalton) reached 25 times, whereas the molecular weight distribution of the polymer does not vary very much, which is in the range of from 1.9 to 2.6, and the isotacticity [mmmm] varies within the scope of 86.0-91.0 (Angew. Chem. Int. Ed. Engl. 1985, 24, 507). In 1989, Herrmann et al. synthesized racemic, silicon-based bridged indene zirconium compounds. Subsequently, Spaleck and Herrmann et al. modified the indene ring with substituents. The polypropylene catalytically produced at a higher temperature and under the action of MAO, reaches or almost reaches the industrial application level in terms of reactivity, molecular weight, molecular weight distribution and isotacticity (up to 98%, m.p. 152° C.) (Angew. Chem. Int. Ed. Engl. 1989, 28, 1511; 1992, 31, 1348). Since then, a series of Group IV metallocene catalysts of bridged biindene ring type and its derivative systems have been successively developed and used in isotactic and catalytic polymerization of propylene (Chem. Rev. 2000, 100, 1253).

Although the reaction conditions such as temperatures, pressures, times, and catalyst concentrations, solvents, auxiliary agents, impurity removal agents, hydrogen molecular regulators and other factors have great influence on the catalytic reaction for generating high isotactic polypropylene, the adjusting and controlling functions of the stereo enantiomorphic site of the racemic structure play an essential and decisive role. These structural features are mainly reflected in five aspects: an indene ring, a substituent on the indene ring, a bridging group, a central metal, and the group which is bonded to the central metal and can initiate chain growth. Those skilled in the art are well aware of the fact that any innovation in one of these five aspects would make the disclosure patentable.

The bridging group connects with two cyclopentadienyl groups, indenyl groups or fluorenyl groups. That is, the two groups are sterically defined. This bridging enhances the rigidity of the ligand structure and plays an important role in the formation of racemic structure characteristic of catalysts. The catalyst with the racemic structure can adjust and control the chain growth of the stereo enantiomorphic sites of propylene well and then produce metallocene polypropylene with high isotacticity.

Although many bridged metallocene catalysts have been reported, not many of them have industrial applications or application prospects. Because industrial applications have high requirements on the isotacticity of metallocene polypropylene. For example, the metallocene polypropylene produced by some companies, can only be used in resin products when its isotacticity [mmmm] is greater than 97%. China's polypropylene products are generally produced by using traditional Natta type catalysts. Some of these catalysts are added with simple metallocene compound components. There are nearly no reports on complete use of metallocene compounds as catalysts because of theoretical and technical difficulties in this regard.

China's polypropylene products are basically produced by using traditional supported Ziegler-Natta catalysts. There are few reports on the use of bridged two-group metallocene catalysts to control the production of polypropylene with high isotacticity because there are still technical difficulties in this regard.

SUMMARY

A first technical problem to be solved by the present disclosure is that the metallocene catalyst in the prior art has the technical problem that the activity is not high enough, to provide a new metallocene compound, wherein the group connecting to the bridge atom of the metallocene compound is a group substituted by an amino group, and/or a group substituted by a metallocene group and/or a substituted metallocene group. The special structure endows a high catalytic activity for the metallocene catalyst containing the metallocene compound; furthermore, with the metallocene catalyst, a high-regularity metallocene polypropylene can be synthesized.

A second technical problem to be solved by the present disclosure is to provide a preparation method of the metallocene compound for solving the first technical problem.

A third technical problem to be solved by the present disclosure is to provide a metallocene catalyst adopting the metallocene compound for solving the first technical problem.

A fourth technical problem to be solved by the present disclosure is to provide a preparation method of the catalyst for solving the third technical problem above.

A fifth technical problem to be solved by the present disclosure is to provide use of the metallocene compound the first technical problem above or the catalyst for solving the third technical problem.

In order to solve the first technical problem above, the present disclosure adopts a technical solution as follows.

Provided is a metallocene compound, having a structure as shown in formula (I):

Z is selected from carbon, silicon, germanium, and tin;

CpIIIis 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 Ri, Rii, and Riiiare the substituents in the corresponding rings;

Ri, Riiand Riiiare the same or different, and each independently selected from hydrogen, and linear or branched, saturated or unsaturated C1-C20hydrocarbyl with or without a heteroatom;

E is NRivor PRiv;

Rivis selected from hydrogen and linear or branched, saturated or unsaturated C1-C20hydrocarbyl, with or without a heteroatom;

M is selected from IVB group metals;

LIVand LVare the same or different, and each independently selected from hydrogen and linear or branched, saturated or unsaturated C1-C20hydrocarbyl with or without a heteroatom; and

n is 1 or 2.

According to the present disclosure, when n is 1, CpIIIis any one of the above cyclopentadienyl, indenyl, or fluorenyl; when n is 2, CpIIIis two of the above cyclopentadienyl, two of the above indenyl, or two of the above fluorenyl, or CpIIIis two of the above cyclopentadienyl, indenyl, or fluorenyl. When n is 2, the two CpIIIgroups can be are the same or different.

According to a preferred embodiment of the present disclosure, the amino is as shown in formula (III):

wherein in formula (III), Raand Rbare the same or different, and each independently selected from hydrogen, C1-C6alkyl, C6-C18aryl, C7-C20arylalkyl, and C7-C20alkylaryl, preferably C1-C6alkyl, C6-C12aryl and C7-C10arylalkyl, and more preferably C1-C4alkyl, phenyl and C7-C9arylalkyl.

According to a preferred embodiment of the present disclosure, the metal in the metallocene group is Fe, and preferably, the metallocene group is ferrocenyl.

According to a preferred embodiment of the present disclosure, in formula (I), RIand RIIare the same or different, and at least one of RIand RIIis selected from amino-substituted C1-C10hydrocarbyl, amino-substituted C1-C10halohydrocarbyl, amino-substituted C1-C10alkoxy and amino-substituted C6-C10phenolic group; and/or at least one of RIand RIIis selected from metallocene group-substituted C1-C10hydrocarbyl, metallocene group-substituted C1-C10halohydrocarbyl, metallocene group-substituted C1-C10alkoxy and metallocene group-substituted C6-C10phenolic group; and/or at least one of RIand RIIis selected from metallocene groups substituted by C1-C10hydrocarbyl, C1-C10halohydrocarbyl, C1-C10alkoxy or C6-C10phenolic group.

According to a preferred embodiment of the present disclosure, in formula (I), RIand RIIare the same or different, and at least one of RIand RIIis selected from amino-substituted C1-C6hydrocarbyl, amino-substituted C1-C6halohydrocarbyl, amino-substituted C1-C6alkoxy, and amino-substituted C6-C8phenolic group; and/or at least one of RIand RIIis selected from metallocene group-substituted C1-C6hydrocarbyl, metallocene group-substituted C1-C6halohydrocarbyl, metallocene group-substituted C1-C6alkoxy, and metallocene group-substituted C6-C8phenolic group; and/or at least one of RIand RIIis selected from metallocene groups substituted by C1-C6hydrocarbyl, C1-C6halohydrocarbyl, C1-C6alkoxy or C6-C8phenolic group.

According to a preferred embodiment of the present disclosure, in formula (I), RIand RIIare the same or different, and at least one of RIand RIIis selected from amino-substituted C1-C6hydrocarbyl; and/or at least one of RIand RIIis selected from metallocene group-substituted C1-C6hydrocarbyl; and/or at least one of RIand RIIis selected from metallocene group substituted by C1-C6hydrocarbyl.

According to a preferred embodiment of the present disclosure, in formula (I), RIand RIIare the same or different, and at least one of RIand RIIis selected from amino-substituted C1-C6linear alkyl; and/or at least one of RIand RIIis selected from metallocene group-substituted C1-C6linear alkyl; and/or at least one of RIand RIIis selected from metallocene group-substituted by C1-C6linear alkyl.

According to a preferred embodiment of the present disclosure, in formula (I), RIand RIIare the same or different, and at least one of RIand RIIis selected from substituted by amino-substituted C1-C4linear alkyl; and/or at least one of RIand RIIis selected from metallocene group-substituted C1-C4linear alkyl; and/or at least one of RIand RIIis selected from metallocene groups substituted by C1-C4linear alkyl.

According to a preferred embodiment of the present disclosure, when only one group of RIand RIIis selected from the groups as defined above, the other group can be selected from C1-C20hydrocarbyl, C1-C20halohydrocarbyl, C1-C20alkoxy and C6-C20phenolic group, preferably C1-C10hydrocarbyl, C1-C10halohydrocarbyl, C1-C10alkoxy and C6-C10phenolic group, more preferably C1-C6hydrocarbyl, C1-C6halohydrocarbyl, C1-C6alkoxy and C6-C8phenolic group, and further preferably C1-C6hydrocarbyl.

According to the present disclosure, Ri, Rii, and Riiirefer to the substituents on the corresponding rings in the above formula. When CpIIIis a cyclopentadienyl group, one or up to four Rican independently connect to the cyclopentadienyl group at any one, two, three, or all four positions (without selection) of the cyclopentadienyl group; when CpIIIis an indenyl group, one or two Rican independently connect to the indenyl group at one of two positions of the five-membered ring or at all two positions without selection; one to four Riican independently connect to the indenyl group at one, two, three, or all four positions (without selection) of the four positions in the six-membered ring; when the benzene ring on which Riiiis a part of the indenyl ring, the definition of Riiiis the same as Rii; when CpIIIis a fluorenyl group, one to four Riiand one to four Riiican independently connect the respective six-membered ring at any one, two, three or all four positions in the two six-membered rings. Ri, Rii, and Riiieach independently refer to hydrogen, linear or branched C1-C20alkyl, C3-C20cycloalkyl, C6-C20aryl, C7-C20alkylaryl, or C7-C20arylalkyl groups, these groups optionally contain one or more heteroatoms, and can also be saturated or unsaturated. Ri, Rii, and Riiimay form a saturated or unsaturated cyclic groups, and these groups may optionally contain one or more heteroatoms.

According to a preferred embodiment of the present disclosure, in formula (II), Ri, Riiand Riiiare the same or different, each independently selected from hydrogen, C1-C20hydrocarbyl, C1-C20haloalkyl, C6-C20aryl, C6-C20haloaryl, C7-C40arylalkyl, C7-C40alkylaryl, C3-C20cycloalkyl, C3-C20heterocycloalkyl, C2-C20alkenyl, C2-C20alkynyl, C1-C20alkoxy, C6-C20phenolic group, C1-C20amino and a group containing a heteroatom selected from groups 13 to 17.

According to a preferred embodiment of the present disclosure, in formula (II), Ri, Riiand Riiiare the same or different, and each independently selected from hydrogen, C1-C10hydrocarbyl, C1-C10haloalkyl, C6-C10aryl, C6-C10haloaryl, C7-C20arylalkyl, C7-C20alkylaryl, C3-C10cycloalkyl, C3-C10heterocycloalkyl, C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, C6-C10phenolic group, C1-C10amino and a group containing a heteroatom selected from groups 13 to 17.

According to a preferred embodiment of the present disclosure, in formula (II), Ri, Riiand Riiiare the same or different, and each independently selected from hydrogen, C1-C6hydrocarbyl, C1-C6haloalkyl, C6-C6aryl, C6-C6haloaryl, C7-C10arylalkyl, C7-C10alkylaryl, C3-C6cycloalkyl, C3-C6heterocycloalkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C6alkoxy, C6-C6phenolic group, C1-C6amino and a group containing a heteroatom selected from groups 13 to 17.

According to a preferred embodiment of the present disclosure, in formula (I), Rivselected from hydrogen and linear or branched, saturated or unsaturated C1-C10hydrocarbyl with or without a heteroatom.

According to a preferred embodiment of the present disclosure, in formula (I), Rivselected from hydrogen and linear or branched, saturated or unsaturated C1-C6hydrocarbyl with or without a heteroatom.

According to a preferred embodiment of the present disclosure, in formula (I), M is selected from Ti, Zr and Hf.

According to a preferred embodiment of the present disclosure, in formula (I), M is Zr.

According to a preferred embodiment of the present disclosure, LIVand LVare the same, and selected from hydrogen, chlorine, methyl, phenyl, benzyl and dimethylamino.

In order to solve the second technical problem, the present disclosure adopts any one of the following technical solutions.

A preparation method of the metallocene compound as mentioned above,

when n is 2, the preparation method comprises:

S1. reacting a H2(CpIII) with an alkali metal-organic compound to form a corresponding [H(CpIII)]−alkali metal salt;

S2. reacting the [H(CpIII)]−alkali metal salt with a RIRIIZX2to form a RIRIIZ[H(CpIII)]2;

S3. reacting the RIRIIZ[H(CpIII)]2with an alkali metal-organic compound to form a corresponding RIRIIZ(CpIII)22−alkali metal salt;

S4. reacting the RIRIIZ(CpIII)22−alkali metal salt with an X2MLIVLVfor salt elimination reaction, to obtain a RIRIIZ(CpIII)2MLIVLV;

when n is 1, the preparation method comprises:

S1. reacting a H2(CpIII) and a H2(E) with an alkali metal-organic compound respectively, to form a corresponding [H(CpIII)]−alkali metal salt and a corresponding [H(E)]−alkali metal salt;

S2. reacting the [H(CpIII)]−alkali metal salt and the [H(E)] alkali metal salt with a RIRIIZX2to form a RIRIIZ[H(CpIII)][H(E)];

S3. reacting the RIRIIZ[H(CpIII)][H(E)] with an alkali metal-organic compound to form a corresponding RIRIIZ(CpIII)(E)2−alkali metal salt;

S4. reacting the RIRIIZ(CpIII)(E)2−alkali metal salt with an X2MLIVLVfor salt elimination reaction, to obtain a RIRIIZCpIIIEMLIVLV.

wherein X is selected from Cl, Br and I;preferably, in S4, RIRIIZ(CpIII)22−alkali metal salt or RIRIIZ(CpIII)(E)2−alkali metal salt directly reacts with X2MLIVLVfor salt elimination reaction without separation.

A preparation method of the metallocene compound as mentioned above, comprising:

preparing the metallocene compound by carrying out a Z hydrogenation reaction between a precursor RIHZ(CpIII)n(E)2-nMLIVLVand a precursor of the RII;

wherein the precursor of the RIIis a molecule containing a multiple bond, preferably, the molecule containing a multiple bond is selected from organic multiple bond molecules, CO and CO2, 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, CEN, C═O, C═P, N═N, C═S, C═C═C, C═C═N, C═C═O, and N═C═N.

According to the present disclosure, the above metallocene compound can be prepared by both options 1 and 2.

According to a preferred embodiment of the present disclosure, the above-mentioned metallocene compound is prepared by option 2. That is, the above-mentioned metallocene compound is prepared by addition reaction of the precursor RIHZ(CpIII)n(E)2-nMLIVLV, RIIHZ(CpIII)n(E)2-nMLIVLVor H2Z(CpIII)n(E)2-nMLIVLVand the molecule containing multiple bonds Z—H. Collins reported the step-by-step synthesis of MeHZ(Cp)2Zr(NMe2)2and MeHZ(Ind)2Zr(NMe2)2(Macromolecules 2001, 34, 3120), that is, the dimer ligands MeHZ(CpH)2and MeHZ(IndH)2are prepared respectively, and then react with Zr(NMe2)4to generate MeHZ(Cp)2Zr(NMe2)2and MeHZ(Ind)2Zr(NMe2)2. This method is similar to the synthesis method as described in the background art wherein a proton of metallocenel ring or non-metallocene compound is removed. The two compounds were reacted with excess Me3ZCl to obtain the compounds MeHZ(Cp)2ZrCl2and MeHZ(Ind)2ZrCl2.

When n is 2, RIHZX2is selected to react with two moles of the H(CpIII) alkali metal salt (when the H(CpIII) is two different groups, each is one mole). The H(CpIII) alkali metal salt is prepared by reacting a ligand H2(CpIII) with an equivalent amount of an alkali metal-organic compound. The alkali metal-organic compound is selected from the group consisting of metal hydride, metal alkyl, alkenyl metal, aryl metal, and amine metal, and preferably metal alkyl; the alkali metal is selected from Li, Na, and K, preferably Li; X is selected from Cl, Br, and I, preferably Cl. The generated RIHZ[H(CpIII)]2does not need to be separated and is directly used in the next reaction. There are two schemes as follows.

a) RIHZ[H(CpIII)]2is reacted with LviiLvivMLIVLVfor eliminating a stable small molecule HLviiior HLvivto obtain RIHZ(CpIII)2MLIVLV, Lviiiand Lvivare leaving groups, which can be the same or different, and selected from hydrogen, alkyl, aryl, amine. Preferably Lviiiand Lvivare the same, and selected from methyl, phenyl and dimethylamino groups.

b) RIHZ[H(CpIII)]2is reacted with two moles of an alkali metal-organic compound to form an alkali metal salt, wherein the definition of the alkali metal-organic compound is the same as above; and then the alkali metal salt is reacted with an X2MLIVLVsalt for salt elimination to obtain RIHZ(CpIII)2MLIVLV, wherein X has the same definition as above.

When n is 1, RIHZX2is selected to react with one mole of H(CPIII) alkali metal salt and one mole of H(E) alkali metal salt. The preparation of H(CpIII) alkali metal salt is the same as that of H(E). The alkali metal salt is prepared by reacting H2(E) with an equivalent amount of an alkali metal-organic compound, and the definition of the alkali metal-organic compound is the same as above. The generated RIHZ[H(CpIII)][H(E)] does not need to be separated and is directly used in the next reaction. There are two schemes as follows:

a) RIHZ[H(CpIII)][H(E)] is reacted with LviiiLvivMLIVLVV for eliminating a stable small molecule HLviiior HLvivto obtain RIHZ(CpIII)(E)MIVLV, wherein Lviiiand Lvivare defined as above.

b) RIHZ[H(CpIII)][H(E)] is reacted with two moles of an alkali metal-organic compound to form an alkali metal salt, wherein the definition of the alkali metal-organic compound is the same as above; and then the alkali metal salt is reacted with an X2MLIVLVsalt for salt elimination to obtain RIHZ(CpIII)2MLIVLV, wherein X has the same definition as above.

Selecting RIIHZX2to prepare RIIHZ(CpIII)n(E)2-nMLIVLVor selecting H2ZX2to prepare H2Z(CpIII)n(E)2-nMLIVLVis similar to the above schemes.

During the preparation of RIHZ(CpIII)n(E)2-nMLIVLV, RIIHZ(CpIII)n(E)2-nMLIVLVor H2Z(CpIII)n(E)2-nMLIVLV, the reaction is carried out in an aprotic solvent The solvent is selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether and dixoane. Among them, H2(CpIII), H2(E), RIHZ[H(CpIII)]2, RIIHZ[H(CpIII)]2, H2Z[H(CpIII)]2, RIHZ[H(CpIII)][H(E)], RIIHZ[H(CpIII)][H(E)] or H2Z[H(CpIII)][H(E)] is reacted with the alkali metal-organic compound at a temperature of −60 to 140° C., the preferred temperature range is −20 to 110° C.; the reaction time is greater than 0.016 h, and the preferred range of the reaction time is 2-100 h. The reaction of RIHZX2, RIIHZX2, H2ZX2with H(CpIII) or H(E) alkali metal salt, and the reaction of X2MLIVLVwith RIHZ[(CpIII)]2, RIIHZ[(CpIII)]2, H2Z[(CpIII)]2, RIHZ[(CpIII)][(E)], RIIHZ[(CpIII)][(E)] or H2Z[(CpIII)][(E)]alkali metal salt are carried out at a temperature of −75 to 100° C., preferably the temperature range is −75 to 60° C.; and the reaction time is greater than 0.1 h, and preferably the reaction time range is 6-100 h. The reaction of RIHZ[H(CpIII)]2, RIIHZ[H(CpIII)]2, H2Z[H(CpIII)]2, RIHZ[H(CpIII)][H(E)], RIIHZ[H(CpIII)][H(E)], or H2Z[H(CpIII)][H(E)] with LviiiLvivMLIVLVfor eliminating a small molecule is carried out at a temperature of 0 to 160° C., and the preferred temperature range is 20 to 140° C.; and the reaction time is greater than 0.1 h, and preferably, the reaction time is in the range of 2-100 h.

The technical solution further provided by the present disclosure is preparing (I) by Z—H addition reaction between the precursor RIHZ(CpIII)n(E)2-nMLIVLV, RIIHZ(CpIII)n(E)2-nMLIVLVor H2Z(CpIII)n(E)2-nMLIVLVand a molecule containing a multiple bond. In the molecule containing a multiple bond, the multiple bond is selected from elements of groups 13 to 16, which may be the same kind of atoms or different kinds of atoms, preferably 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, N═C═N. The Z—H addition reaction requires the participation of a catalyst. The catalyst is selected from transition metal catalysts and Lewis acid catalysts, preferably platinum catalysts of the transition meta catalysts and B(C6F5)3catalysts of the Lewis acids. In order to better achieve the purpose of the present disclosure, a catalyst that preferably has no effect on LIVand LVin the aforementioned precursor or does not affect the reaction of Z—H with multiple bonds is required. This means that when the catalyst interacts with the LIVand LLVin the aforementioned precursors and affects the addition reaction of Z—H with multiple bonds, the LIVand LLVgroups need to undergo a group conversion reaction through the prepared related compounds. It is converted into a group that does not affect the reaction of Z—H with multiple bond. For example, when LIVand LVare methy, the B(C6F5)3catalyst will complex with the methyl to form [MeB(C6F5)3], and thus lose the catalytic effect. Then LIVand LVneed to be converted to NMe2or other non-reactive group.

The reaction of Z—H in the precursor RIHZ(CpIII)n(E)2-nMLIVLV, RIIHZ(CpIII)n(E)2-nMLIVLVor H2Z(CpIII)n(E)2-nMLIVLVwith the molecule containing a multiple bond is carried out in a protic solvent. The solvent may be selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether and dioxane. The amount of catalyst used in the reaction is 0.00001-50% preferably 0.01-20% of the total mass of the reactants; the reaction is carried out at a temperature of −30 to 140° C., and the preferred temperature range is 0 to 90° C.; the reaction time is more than 0.1 h, and the reaction time is preferably in the range of 2-50 h. The target product (I) is separated or purified by recrystallization.

According to the present disclosure, “Z” is preferably silicon.

According to a preferred embodiment of the present disclosure, the Z hydrogenation reaction is carried out in the presence of a catalyst selected from transition metal catalysts and Lewis acid catalysts, preferably platinum catalysts of transition metal catalysts and B(C6F5)3of Lewis acid catalysts.

According to a preferred embodiment of the present disclosure, the 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.

According to a preferred embodiment of the present disclosure, the temperature of the Z hydrogenation reaction is −30 to 140° C., preferably 0 to 90° C.

According to a preferred embodiment of the present disclosure, the reaction time of the Z hydrogenation reaction is greater than 0.1 h, preferably 2-50 h.

According to a preferred embodiment of the present disclosure, the obtained precursor is separated or purified by recrystallization, and the solvent for the recrystallization is an aprotic solvent; preferably, it is selected from linear or branched alkane compounds and cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds; further preferably, selected from toluene, xylene, hexane, heptane, cyclohexane and methylcyclohexane.

According to a preferred embodiment of the present disclosure, the precursor RIHZ(CpIII)n(E)2-nMLIVLVis prepared by a one-pot method of chemical reaction.

According to a preferred embodiment of the present disclosure, when n is 2, the preparation method of the precursor RIHZ(CpIII)n(E)2-nMLIVLVcomprises:

step 1), reacting a H2(CpIII) with an alkali metal-organic compound to form a corresponding [H(CpIII)] alkali metal salt;

step 2), reacting the [H(CpIII)]−alkali metal salt with a RIHZX2to form a RIHZ[H(CpIII)]2;

step 3), directly reacting the RIHZ[H(CpIII)]2without separation, with a LviiiLvivMLIVLVfor eliminating a stable small molecule Lviiior Lviv, to obtain the precursor RIHZ(CpIII)2MLIVLV,

and/or, directly reacting the RIHZ[H(CpIII)]2without separation, with an alkali metal-organic compound to form an alkali metal salt; the obtained alkali metal salt is then reacted with an X2MLIVLVfor salt elimination reaction, to obtain the precursor RIHZ(CpIII)2MLIVLV; and

when n is 1, the preparation method of the precursor RIHZ(CpIII)n(E)2-nMLIVLVcomprises:

step 1), reacting a H2(CpIII) and a H2(E) respectively with an alkali metal-organic compound to form a corresponding [H(CpIII)]−alkali metal salt and a corresponding [H(E)]−alkali metal salt;

step 2), reacting the [H(CpIII)]−alkali metal salt and the [H(E)]−alkali metal salt with RIHZX2to form a RIHZ[H(CpIII)][H(E)];

step 3), directly reacting the RIHZ[H(CpIII)][H(E)] without separation, with a LviiiLvivMLIVLVby eliminating a stable small molecule Lviiior LVviv, to obtain the precursor RIHZCpIIIEMLIVLV;

and/or, directly reacting the RIHZ[H(CpIII)][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 X2MLIVLVfor salt elimination reaction, to obtain the precursor RIHZCpIIIEMLIVLV;

wherein X is selected from Cl, Br and I.

According to the present disclosure, when one pot method is used, RIis formed by the addition reaction of the Z—H bond in the precursor RIIHZ(CpIII)n(E)2-nMLIVLVand the multiple bond in a molecule containing multiple bond, and RIIis formed by the addition reaction of the Z—H bond in the precursor RIHZ(CpIII)n(E)2-nMLIVLVand a multiple bond in a molecule containing multiple bond, or both RIand RIIare formed by the addition reaction of Z—H bond in the precursor H2Z(CpIII)n(E)2-nMLIVLVand a multiple bond in a molecule containing multiple bond; the multiple bond molecule is an organic multiple bond molecule, CO or CO2, preferably an organic multiple bond molecule. Thus, RIand RIIcan be the same or different.

According to a preferred embodiment of the present disclosure, in each step, a reaction temperature of the reaction is −100° C. to 140° C., preferably −85° C. to 110° C.; and/or, ae reaction time is greater than 0.016 h, preferably 2 to 100 h.

According to a preferred embodiment of the present disclosure, in each step, the reaction materials are mixed at −100° C. to −20° C., preferably −85° C. to −10° C., react at 10° C. to 50° C., preferably 20° C. to 35° C. for 1 h to 100 h, preferably 5 h to 50 h.

According to a preferred embodiment of the present disclosure, in each step, the reaction is carried out in an aprotic solvent selected from linear or branched alkane compounds, cycloalkane compounds, aromatic compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether and dioxane.

According to a preferred embodiment of the present disclosure, the alkali metal-organic compound selected from hydrogenated metal, alkyl metal, alkenyl metal, aromatic metal and amine metal, preferably alkyl metal, and more preferably C1-C6alkyl metal.

According to a preferred embodiment of the present disclosure, the alkali metal is selected from Li, Na and K, preferably Li.

In order to solve the third technical problem, the present disclosure adopts the following technical solution.

A catalyst for α-olefin polymerization reaction, comprising: the metallocene compound as mentioned above or the metallocene compound prepared according to the above preparation method, a cocatalyst and a carrier.

According to a preferred embodiment of the present disclosure, 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 anions 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.

According to a preferred embodiment of the present disclosure, the alkyl aluminum comprises trimethyl aluminum and triethyl aluminum.

According to a preferred embodiment of the present disclosure, the perfluoroaryl group is selected from perfluorophenyl, perfluoro naphthyl, perfluoro biphenyl and perfluoroalkyl phenyl, and the cation is selected from N, N-dimethylphenylammonium ion, triphenylcarboonium ion, trialkyl ammonium ion and triarylammonium ion.

According to a preferred embodiment of the present disclosure, the content of the metallocene compound in the catalyst is 0.001 mass % to 10 mass %, preferably 0.01 mass % to 1 mass %, based on M element; and/or the molar ratio of Al element in the cocatalyst to M element in the metallocene compound is (1-500):1, preferably (50-300):1

According to a preferred embodiment of the present disclosure, the catalyst has an asymmetric structure. The asymmetric structure can be multi-layered, which can refer to the asymmetry of RIand RIIin metallocene compounds, the asymmetric structure formed by the interaction between metallocene compounds and additives, or the carrier loading after the interaction between metallocene compounds and additives to further strengthen the asymmetry.

In order to solve the fourth technical problem above, the technical solution adopted by the present disclosure is as follows.

A method for preparing the above-mentioned catalyst includes: combining the metallocene compound, the co-catalyst and the carrier under the action of a solvent to form the catalyst.

According to a preferred embodiment of the present disclosure, the conditions of the combination include: the temperature of the combination is −40° C. to 200° C., preferably 40° C. to 120° C.; the time of the combination is greater than 0.016 h, preferably 2 h-100 h.

According to a preferred embodiment of the present disclosure, the preparation method of the above-mentioned catalyst comprises:

i) mixing the co-catalyst, the carrier and the solvent to obtain a mixture A;

ii) mixing the mixture A with the metallocene compound to obtain a mixture B; preferably, mixting the metallocene compound in a solvent first, to form a mixture which is then mixed with the mixture A;

iii) separating a solid from the mixture B, and drying the solid to prepare the catalyst.

According to a preferred embodiment of the present disclosure, in step i), the carrier is calcinated. Preferably, conditions of the calcination treatment include: a calcination temperature of 50° C. to 700° C., and a calcination time of 0.5 h to 240 h.

According to a preferred embodiment of the present disclosure, the mixture A is heated. Preferably, conditions of the heating treatment include: a heating temperature of 30° C. to 110° C., and a heating time of 0.1 h to 100 h.

According to a preferred embodiment of the present disclosure, in step iii), conditions of the drying treatment include: a drying temperature of 30° C. to 110° C., and a drying time of 0.1 h to 100 h.

According to a preferred embodiment of the present disclosure, the solid is washed before the drying treatment, preferably the solid is washed with the solvent, and more preferably, the solvent after washing is washed until the solvent does not contain metal ions.

In order to solve the fifth technical problem above, the technical solution adopted by the present disclosure is as follows.

Use of the above-mentioned metallocene compound or the metallocene compound prepared according to the above-mentioned preparation method or the above-mentioned catalyst or the above-mentioned preparation method in the field of α-olefin polymerization.

According to a preferred embodiment of the present disclosure, polymerization reaction of the α-olefin is carried out in the presence of the above-mentioned metallocene compound or the metallocene compound prepared according to the above-mentioned preparation method or the above-mentioned catalyst or the above-mentioned preparation method, to obtain poly-α-olefin.

According to a preferred embodiment of the present disclosure, the polymerization reaction is carried out under a solvent-free condition.

According to a preferred embodiment of the present disclosure, conditions of the polymerization reaction include: a reaction temperature of −50° C. to 200° C., preferably 30° C. to 100° C.; and a reaction time of 0.01 h to 60 h, preferably 0.1 h to 10 h.

According to a preferred embodiment of the present disclosure, the metallocene catalyst or metallocene catalyst system is used in an amount of 0.001 mg to 1000 mg, preferably 0.01 mg to 200 mg, and more preferably 0.1 mg to 20 mg per gram of α-olefin.

In some specific embodiments of the present disclosure, the α-olefin is propylene. When the α-olefin is propylene, the bulk polymerization reaction can be carried out with propylene and hydrogen as raw materials (this bulk polymerization reaction can be carried out in a tank reactor or a tubular reactor; it can be carried out batchwise or continuously), the amount of hydrogen can be 0 to 0.10 g/g propylene, preferably 0.00001 to 0.10 g/g propylene. In addition, when polymerizing propylene, impurity breakers can be used. The impurity breaker is a substance commonly used in the field, and its specific dosage can be 0-100 mmol/g propylene, preferably 0.001-10 mmol/g propylene.

In some specific embodiments of the present disclosure, the α-olefin is ethylene. When the α-olefin is ethylene, the gas phase polymerization reaction is carried out, and the reaction temperature is 0-200° C., preferably 20-140° C.; and/or, the reaction time is 0.016-60 h, preferably 0.1-20 h; and/or, ethylene The pressure is 0.1-15 MPa, preferably 0.2-10 MPa, and/or the amount of catalyst is 0.00001-100 mg/g ethylene, and/or the amount of impurity removal agent is 0-100 mmol/g ethylene, and/or hydrogen The dosage is 0-0.01 g/g ethylene.

In the present disclosure, the term “hydrocarbyl” may be alkyl, aryl, alkylaryl, arylalkyl, alkynyl, alkenyl and the like.

In the present disclosure, the term “heteroatom” may refer to a heteroatom such as oxygen, sulfur, nitrogen, and phosphorus.

In the present disclosure, the term “substituted” may refer to substitution by a substituent, which may be selected from halogens, non-carbon oxo acid groups and their derivatives, and optionally substituted alkyl, aralkyl and aryl groups. For example, a group substituted with an alkyl group, an aryl group, an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an oxa group, a carboxyl group, a thia group, a sulfur oxyacid, a halogen group, and a combination thereof.

In the present disclosure, the term “one-pot method” may refer to a continuous multi-step synthesis reaction carried out in the same reactor.

In the present disclosure, “Tol” means toluene.

The beneficial effects of the present disclosure are at least:

1) At least one of the two different groups on the bridging atom of the metallocene compound used in the present disclosure is an amine substituted group and/or a metallocene substituted group and/or a substituted metallocene group, and thus it can promote the formation of a metallocene catalyst with a racemic structure. When combined with a co-catalyst and a carrier, it can realize the chain growth of olefins such as propylene and ethylene that is controlled by the stereo enantiomorphic sites to form high isotacticity metallocene polypropylene or metallocene polyethylene.

2) The method for preparing metallocene compounds provided by the present disclosure can effectively carry out group transformations of bridging atoms, and prepare bridging metallocene compounds with various structures and compositions. The bridged metallocene compound obtained after the hydrogenation of the bridged atom is combined with the cocatalyst and the carrier to form a metallocene catalyst, which has good thermal stability and catalytic activity, and can be used for the polymerization of ethylene or propylene and other alpha-olefins.

DETAILED DESCRIPTION OF THE EMBODIMENTS

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

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

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

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

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

Preparation of the metallocene compound as shown in formula 1:

40 mmol of 4-phenyl-2-methylindene was weighed and dissolved in 200 mL of Et2O, 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.

20 mmol of Me(PhMeNH2CH2CH2C)SiCl2was 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(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H5)2, which was weighed 8.2 mmol, and the yield was 41%.

5 mmol of Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H5)2was 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.

5 mmol ZrCl4was 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(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2]ZrCl2as shown in formula 1, which was weighed 1.2 mmol, and the yield was 24%.

The preparation methods of the metallocene compound of formula 12 to formula 14 were also the similar to this, except that Me(PhMeNCH2CH2CH2)SiCl2in the second step was replaced with Me[CpFe(C5H4)CH2CH2]SiCl2, Me[CpFe(C5H4)CH2CH2CH2]SiCl2, Me[CpFe(C5H4)CH2]SiCl2respectively, and finally zirconocene compounds Me[CpFe(C5H4)CH2CH2]Si(4-Ph-2-MeC9H4)2ZrCl2(formula 12, which was weighed 1.0 mmol, yield 20%), Me[CpFe(C5H4)CH2CH2CH2]Si(4-Ph-2-MeC9H4)2ZrCl2(formula 13, which was weighed 1.3 mmol, yield 26%), Me[CpFe(C5H4)CH2]Si(4-Ph-2-MeC9H4)2ZrCl2(formula 14, which was weighed 0.8 mmol, yield 16%) were obtained.

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(PhMeNCH2CH2CH2)SiCl2in the second step was replaced with Me[CpFe(C5H4)CH2CH2]SiCl2, finally to obtain zirconocene compound Me[CpFe(C5H4)CH2CH2]Si(4-(4-tBuC6H4)-2-MeC9H4)2ZrCl2(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-tBuC6H4C9H4)2ZrCl2(MS-1)

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.

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 C41H48Cl2SiZr(Mr=731.04): theoretical value: C, 67.36; H, 6.62; measured value: C, 67.54, H, 6.56.

Synthesis Example 2

Rac-MS-1 (1.45 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Me2NCH═CH2(0.156 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 3

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.

Synthesis Example 4

The implementation steps were the same as Synthesis Example 2, wherein Me2NCH═CH2was replaced with PhMeNCH═CH2(0.293 g, 2.2 mmol), and finally 1.65 g (95.9%) of yellow solid rac-MS-1b was obtained.

Synthesis Example 5

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was replaced with Me2NCH2CH═CH2(0.187 g, 2.2 mmol), and finally 1.35 g (83.2%) of yellow solid rac-MS-1c was obtained.

Synthesis Example 6

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was replaced with PhMeNCH2CH═CH2(0.324 g, 2.2 mmol), and finally 1.61 g (92.3%) of yellow solid rac-MS-1d was obtained.

Synthesis Example 7

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was replaced with iPr2NCH2CH═CH2(0.310 g, 2.2 mmol), and finally a yellow solid rac-MS-1e 1.54 g (88.8%) was obtained.

Synthesis Example 8

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was replaced with iBuMeNCH2CH2CH═CH2(0.310 g, 2.2 mmol), and finally a yellow solid rac-MS-if 1.57 g (90.62%) was obtained.

Synthesis Example 9

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was replaced with PhMeNCH2CH2CH═CH2(0.354 g, 2.2 mmol), and finally a yellow solid rac-MS-1 g 1.64 g (92.52%) was obtained.

Synthesis Example 10

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was replaced with iPrEtNCH2CH2CH═CH2(0.310 g, 2.2 mmol), and finally a yellow solid rac-MS-1h 1.57 g (90.61%) was obtained.

Synthesis Example 11

The implementation steps were the same as Example 1, wherein Me2NCH═CH2was 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(C5H4).

Synthesis Example 12

The implementation steps were the same as in Example 1, wherein Me2NCH═CH2was replaced of FcCH═CH2(0.424 g, 2 mmol), and finally an orange-red solid rac-MS-1j 1.63 g(87.17%). In FcCH═CH2, Fc=CpFe(C5H4).

Synthesis Examples 13 and 14 Preparation of Precursors

Preparation of Hydrogen Silicon Bridged Bisindenyl Zirconocene Compound MeHSi(2-Me-7-p-tBuC6H4C9H4)2Zr(NMe2)2(rac-MS-2)

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.

Synthesis Example 13

Rac-MS-2 (1.49 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeNCH═CH2(0.293 g, 2.2 mmol) and B(C6F5)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%).

Synthesis Example 14

The implementation steps were the same as Example 13, wherein PhMeNCH═CH2was replaced with FcCH═CH2(0.424 g, 2 mmol), and finally an orange-red solid meso-MS-1a 1.4 g(87.7%). In FcCH═CH2, Fc=CpFe(C5H4).

Synthesis Examples 15 and 16 Preparation of Precursors

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.

Synthesis Example 15

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeNCH═CH2(0.293 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 16

The implementation steps were the same as Synthesis Example 13, wherein PhMeNCH═CH2was replaced with FcCH═CH2(0.424 g, 2 mmol), and finally an orange-red solid rac-MS-3b 1.53 g (86.7%) was obtained. In FcCH═CH2, Fc=CpFe(C5H4).

Preparation of Precursors of Synthesis Examples 16 and 17

Preparation of Hydrogen Silicon Bridged Bisfluorenyl Zirconocene Compound MeHSiFlu2ZrCl2(MS-4)

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.

Synthesis Example 17

MS-4 (1.07 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeNCH═CH2(0.293 g, 2.2 mmol) and B(C6F5)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%).

Synthesis Example 18

The implementation steps were the same as Synthesis Example 17, wherein PhMeNCH═CH2was replaced with FcCH═CH2(0.424 g, 2 mmol), and finally an orange-red solid MS-4b 1.32 g (88.4%) was obtained. In FcCH═CH2, Fc=CpFe(C5H4).

Synthesis Example 19

Preparation of Me[(PhMeN(CH2)5)]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH2); CH═CH2(0.388 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 20

Preparation of Me[PhMeN(CH2)8]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH2)6CH═CH2(0.480 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 21

Preparation of Me[PhMeN(CH2)12]Si(2-Me-7-PhC9H4)ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH2)9CH═CH2(0.573 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 22

Preparation of Me[PhMeN(CH2)15]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH2)12CH═CH2(0.666 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 23

Preparation of Me[p-ClC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. p-ClC6H4MeN(CH2)3CH═CH2(0.461 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 24

Preparation of Me[p-MeOC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. p-MeOC6H4MeN(CH2)3CH═CH2(0.454 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 25

Preparation of Me[Fc(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH2)3CH═CH2(0.559 g, 2.2 mmol) (note: Fc=CpFe(C5H4)) and B(C6F5)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.

Synthesis Example 26

Preparation of Me(Fc(CH2)8)Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH2)6CH═CH2(0.652 g, 2.2 mmol)(note: Fc=CpFe(C5H4)) and B(C6F5)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.

Synthesis Example 27

Preparation of Me[Fc(CH2)12]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH2)10CH═CH2(0.775 g, 2.2 mmol) (note: Fc=CpFe(C5H4)) and B(C6F5)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.

Synthesis Example 28

Preparation of Me[Fc(CH2)15]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH2)13CH═CH2(0.868 g, 2.2 mmol) (note: Fc=CpFe(C5H4)) and B(C6F5)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.

Synthesis Example 29

The metallocene compound with RIbeing methyl group and RIIbeing an alkyl group can be synthesized by referring to the bridged SiH group addition method.

Preparation of MenBuSi(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. CH3CH2CH═CH2(0.123 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 30

Preparation of Me[n-CH3(CH2)7]Si(2-Me-7-PhC9H4)2ZrCl2

Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. CH3(CH2)5CH═CH2(0.247 g, 2.2 mmol) and B(C6F5)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.

Synthesis Example 31

Preparation of MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2

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)ZrCl22.88 g (60.0%).

Synthesis Example 32

Preparation of Me[Fc(CH2)5]Si(4-Ph-2-MeC9H4)(NtBu)ZrCl2

MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2(0.96 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. Fc(CH2)3CH═CH2(0.559 g, 2.2 mmol)(note: Fc=CpFe(C5H4)) and B(C6F5)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(CH2)5]Si(4-Ph-2-MeC9H4)(NtBu)ZrCl21.21 g (82.1%) was obtained.

B. Preparation of Metallocene Catalysts

Preparation Example 1

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).

Preparation Example 2

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.

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.

Preparation Example 3

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.

Preparation Example 4

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

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.

Preparation Example 6

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).

Preparation Example 7

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).

Preparation Example 8

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).

Preparation Example 9

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).

Preparation Example 10

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).

Preparation Example 11

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).

Preparation Example 12

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).

Preparation Example 13

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).

Preparation Example 14

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).

Preparation Example 15

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.

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

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

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).

Preparation Example 18

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).

Preparation Example 19

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).

Preparation Example 20

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

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.

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.

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).

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).

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).

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).

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).

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

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

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.

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.

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[(PhMeN(CH2)5)]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3c-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[PhMeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrC2was taken, to obtain a catalyst rac-MS-3d-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[PhMeN(CH2)12]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3e-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[PhMeN(CH2)15]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3f-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[p-ClC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3 g-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[p-MeOC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4) ZrCl2was taken, to obtain a catalyst rac-MS-3h-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3i, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me(Fc(CH2)5)Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3j, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH2)12]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3k-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH2)15]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3l, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound MenBuSi(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3m-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[n-CH3(CH2);]Si(2-Me-7-PhC9H4)2ZrCl2was taken, to obtain a catalyst rac-MS-3n-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and compound MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2was taken, to obtain a catalyst rac-MS-3o-C, wherein zirconium content was 0.268% (29.4 μmol/g).

Al/Zr ratio was controlled to be 200:1 and zirconocene compound Me[Fc(CH2)5]Si(4-Ph-2-MeC9H4)(NtBu)ZrCl2was taken, to obtain a catalyst rac-MS-3p-C, wherein zirconium content was 0.268% (29.4 μmol/g).

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

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.

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.)

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.

Finally, 23.5 g of polymer was obtained, and the calculated activity was 2.35×106g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 92 g of polymer was obtained, and the calculated polymerization activity was 4.00×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.4%. The melting point test value was 151.33° C. (Note: PP analysis was selective.)

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

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.

Finally, 64 g of polymer was obtained, and the calculated polymerization activity was 2.78×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 57 g of polymer was obtained, and the calculated polymerization activity was 2.45×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 80 g of polymer was obtained, and the calculated polymerization activity was 3.48×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.3%. The melting point test value was 149.43° C.

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

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.

Finally, 52 g of polymer was obtained, and the calculated polymerization activity was 2.26×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 43 g of polymer was obtained, and the calculated polymerization activity was 1.85×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 450 g of polymer was obtained, and the calculated polymerization activity was 1.098×108g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.6%. The melting point test value was 151.4° C.

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

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.

Finally, 860 g of polymer was obtained, and the calculated polymerization activity was 1.772×108g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 152.2/161.4° C.

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

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.

Finally, 80 g of polymer was obtained, and the calculated polymerization activity was 3.186×107g(PP)·mol(Zr)·h−1.

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

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.

Finally, 35 g of polymer was obtained, and the calculated polymerization activity was 2.389×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 600 g of polymer was obtained, and the calculated polymerization activity was 2.206×108g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.7%. The melting point test value was 151.83/152.2° C.

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

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.

Finally, 270 g of polymer was obtained, and the calculated polymerization activity was 1.613×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 390 g of polymer was obtained, and the calculated polymerization activity was 3.106×108g(PP)·mol(Zr)·h−1. Mn was 47736, Mw was 146937, and PDI value was 3.08, all of them were measured by the high temperature GPC.

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

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.

Finally, 205 g of polymer was obtained, and the calculated polymerization activity was 1.633×108g(PP)·mol−1(Zr)·h−1. The melting point test value was 154.03° C.

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

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.

Finally, 540 g of polymer was obtained, and the calculated polymerization activity was 4.301×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 1.195×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 45 g of polymer was obtained, and the calculated polymerization activity was 5.376×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 82 g of polymer was obtained, and the calculated polymerization activity was 9.797×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 92 g of polymer was obtained, and the calculated polymerization activity was 1.099×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 530 g of polymer was obtained, and the calculated polymerization activity was 4.221×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 610 g of polymer was obtained, and the calculated polymerization activity was 4.859×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 533 g of polymer was obtained, and the calculated polymerization activity was 4.245×108g(PP)·mol−1(Zr)·h−1. The melting point test value was 155.46° C.

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

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.

Finally, 405 g of polymer was obtained, and the calculated polymerization activity was 3.226×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 530 g of polymer was obtained, and the calculated polymerization activity was 4.221×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 145 g of polymer was obtained, and the calculated polymerization activity was 1.732×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 461 g of polymer was obtained, and the calculated polymerization activity was 1.106×107g(PP)·mol−1(Zr)·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 temperature13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 153.1° C.

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

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.

Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.788×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.1%. The melting point test value was 154.9° C.

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

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.

Finally, 91 g of polymer was obtained, and the calculated polymerization activity was 1.641×107g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 424 g of polymer was obtained, and the calculated polymerization activity was 2.112×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 98.9%. The melting point test value was 155.4° C.

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

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.

Finally, 447 g of polymer was obtained, and the calculated polymerization activity was 2.294×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.2%. The melting point test value was 157.1° C.

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

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.

Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.223×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.4%. The melting point test value was 159.1° C.

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

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.

Finally, 472 g of polymer was obtained, and the calculated polymerization activity was 2.252×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.5%. The melting point test value was 161.4° C.

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

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.

Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.489×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 97.2%. The melting point test value was 147.9° C.

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

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.

Finally, 471 g of polymer was obtained, and the calculated polymerization activity was 2.437×107g(PP)·mol−1(Zr)·h−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.

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

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.

Finally, 487 g of polymer was obtained, and the calculated polymerization activity was 2.336×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 96.6%. The melting point test value was 144.7° C.

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

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.

Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.159×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 97.6%. The melting point test value was 152.9° C.

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

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.

Finally, 459 g of polymer was obtained, and the calculated polymerization activity was 2.573×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 95.6%. The melting point test value was 147.9° C.

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

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.

Finally, 485 g of polymer was obtained. The PDI value measured by high temperature GPC was 2.028; the isotacticity measured by high temperature13C NMR spectrum was [mmmm] 96.3%. The melting point test value was 148.5° C.

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 temperature13C NMR spectrum was [mmmm] 92.6%. The melting point test value was 145.1° C.

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

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.

Finally, 418 g of polymer was obtained, and the calculated polymerization activity was 2.434×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 96.7%. The melting point test value was 148.8° C.

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

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.

Finally, 401 g of polymer was obtained, and the calculated polymerization activity was 2.248×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 92.4%. The tested melting point was 140.2° C.

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

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.

Finally, 491 g of polymer was obtained, and the calculated polymerization activity was 2.752×107g(PP) mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 97.2%. The melting point test value was 148.7° C.

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.

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.

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.

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.

Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 6.8×106g(PE)·mol−1(Zr)·h−1.

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.

Finally, 16 g of polymer was obtained, and the calculated polymerization activity was 1.08×107g(PE)·mol−1(Zr)·h−1.

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.

Finally, 35 g of polymer was obtained, and the calculated polymerization activity was 6.99′106g(PE)·mol−1(Zr)·h−1.

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.

Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 0.88×106g(PE)·mol−1(Zr)·h−1.

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.

Finally, 21 g of polymer was obtained, and the calculated polymerization activity was 4.45×106g(PE)·mol−1(Zr)·h−1.

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.

Finally, 36 g of polymer was obtained, and the calculated polymerization activity was 2.74×107g(PE)·mol−1(Zr)·h−1.

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.

Finally, 54 g of polymer was obtained, and the calculated polymerization activity was 1.22×107g(PE)·mol−1(Zr)·h−1.

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.

Finally, 62 g of polymer was obtained, and the calculated polymerization activity was 1.41×107g(PE)·mol−1(Zr)·h−1.

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

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.

Finally, 91 g of the polymer was obtained, and the calculated polymerization activity was 9.20×106g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.3%. The melting point test value was 157.63° C.

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

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.

Finally, 132 g of polymer was obtained, and the calculated polymerization activity was 4.33×106g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 98.6%. The melting point test value was 152.3° C.

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

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.

Finally, 412 g of polymer was obtained, and the calculated polymerization activity was 3.37×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 99.1%. The melting point test value was 154.4° C.

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

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.

Finally, 478 g of polymer was obtained, and the calculated polymerization activity was 1.54×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 153.2° C.

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

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.

Finally, 135 g of polymer was obtained, and the calculated polymerization activity was 4.37×107g(PP)·mol−1(Zr)·h−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 temperature13C NMR spectrum was [mmmm] 96.7%. The melting point test value was 147.83/150.2° C.

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

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.

Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 1.52×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 455 g of polymer was obtained, and the calculated polymerization activity was 1.47×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 492 g of polymer was obtained, and the calculated polymerization activity was 1.59×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 421 g of polymer was obtained, and the calculated polymerization activity was 1.36×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 387 g of polymer was obtained, and the calculated polymerization activity was 1.25×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 418 g of polymer was obtained, and the calculated polymerization activity was 1.35×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 441 g of polymer was obtained, and the calculated polymerization activity was 1.43×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 427 g of polymer was obtained, and the calculated polymerization activity was 1.38×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 434 g of polymer was obtained, and the calculated polymerization activity was 1.41×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 395 g of polymer was obtained, and the calculated polymerization activity was 1.27×108g(PP)·mol−1(Zr)·h−1.

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

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.

Finally, 352 g of polymer was obtained, and the calculated polymerization activity was 1.14′108g(PP)·mol−1(Zr)·h−1.

Comparative Example 1

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

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.

Finally, 425 g of polymer was obtained, and the calculated polymerization activity was 1.38×108g(PP)·mol−1(Zr)·h−1.

Comparative Example 2

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

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.

Finally, 420 g of polymer was obtained, and the calculated polymerization activity was 1.36×108g(PP)·mol−1(Zr)·h−1.

Comparative Example 3

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

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.

Finally, 268 g of polymer was obtained, and the calculated polymerization activity was 8.68×107g(PP)·mol−1(Zr)·h−1.

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

TABLE 3Polymerization product propertiesCatalystReactionIsotac-MeltingAl/ZrAl/ZrMetallocene compoundCatalystPDIticitypointItemCatalystratioratioRIRII(CpIII)n(E)2−nactivityMnMwvalue(%)(° C.)ExampleSC-9100:1549:1MeiPr2NH2CH2CH2C(4-Ph-2-22.521759414197452.38699.5161.433MeC9H4)2ExampleSC-10100:1549:1MeiBuMeNH2CH2CH2C(4-Ph-2-24.891559674307412.76297.2147.934MeC9H4)2ExampleSC-11100:1549:1MeiBuEtNH2CH2CH2C(4-Ph-2-24.371521344165722.73897.5148.135MeC9H4)2ExampleSC-12100:1549:1MeiPrEtNH2CH2CH2C(4-Ph-2-23.361428793966542.77696.6144.736MeC9H4)2ExampleSC-13100:1549:1Me2NH2CH2CiBuMeNH2CH2CH2C(4-Ph-2-21.591626783967892.43997.6152.937MeC9H4)2ExampleSC-14100:1—MeFcCH2CH2(4-Ph-2-25.731826684067692.22695.6147.938MeC9H4)2ExampleSC-15——MeFcCH2CH2(4-Ph-2-———2.02896.3148.539MeC9H4)2ExamplePrep-——MeFcCH2CH2(4-Ph-2-———2.67892.6145.140arationMeC9H4)2Exam-ple 16ExampleSC-16100:1—MeFcCH2CH2CH2(4-Ph-2-24.341727614354322.52096.7148.841MeC9H4)2ExampleSC-17100:1—MeFcCH2(4-Ph-2-22.481237584673273.77692.4140.242MeC9H4)2ExampleSC-18100:1—MeFcCH2CH2(4-(4-27.521864694042192.16897.2148.743tBuC6H4)-2-MeC9H4)2Note:In Tables 1-3, the unit of catalyst activity in Examples 1-43 is 106g(PP) · mol − 1(Zr) · h−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 C2-C4groups or metallocene-substituted C1-C3groups, 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 4CatalystReactionMetallocene CompoundCatalystItemCatalystAl/Zr ratioAl/Zr ratioRIRII(CpIII)n(E)2−nactivityExamplerac-MS-1b-C200:1200:1MePhMeNCH2CH2(2-Me-7-p-tBuC6H4C9H4)26.844Examplerac-MS-1b-C200:1200:1MePhMeNCH2CH2(2-Me-7-p-tBuC6H4C9H4)210.845Examplerac-MS-1b-C200:1200:1MePhMeNCH2CH2(2-Me-7-p-tBuC6H4C9H4)26.9946Examplerac-MS-1j-C50:1200:1MeFcCH2CH2(2-Me-7-p-tBuC6H4C9H4)20.8847Examplerac-MS-3a-C100:1200:1MePhMeNCH2CH2(2-Me-7-PhC9H4)24.4548Examplerac-MS-3b-C200:1200:1MeFcCH2CH2(2-Me-7-PhC9H4)227.449Examplerac-MS-4a-C200:1200:1MePhMeNCH2CH2Flu212.250Examplerac-MS-4b-C200:1200:1MeFcCH2CH2Flu214.151Note:The unit of catalyst activity in Examples 44-51 is 106g(PE) · mol−1(Zr) · h−1.According to the data in Table 4:1)When the substituent on the bridging atom in the metallocene compound contains an amine-substituted C2group or a metallocene-substituted C2group, 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 5Polymerization product propertyCatalystReactionMeltingratioratioMetallocene compoundCatalystPDIIsotacticitypointItemCatalystAl/ZrAl/ZrRIRII(CpIII)n(E)2−nactivityMnMwvalue(%)(° C.)Examplerac-MS-1b-200:1500:1MePhMeNCH2CH2(2-Me-7-p-9.21339453423752.5799.3157.6352CtBuC6H4C9H4)2Examplerac-MS-1j-200:1200:1MeFcCH2CH2(2-Me-7-p-4.3312736136.4312.8398.6152.353CtBuC6H4C9H4)2Examplerac-MS-1b-200:1549:1MePhMeNCH2CH2(2-Me-7-p-33.71734533942572.27399.1154.454CtBuC6H4C9H4)2Examplerac-MS-1b-200:1549:1MePhMeNCH2CH2(2-Me-7-p-1541354273978922.93898.4153.255CtBuC6H4C9H4)2Examplerac-MS-1j-200:11707:1MeFcCH2CH2(2-Me-7-p-43.7824512135092.5996.7150.256CtBuC6H4C9H4)2Note:In Table 5, the unit of catayst activity in Examples 52-58 is 106g(PP) · mol−1(Zr) · h−1.According to the data in Table 5:1)When the substituent on the bridging atom in the metallocene compound contains an amine-substituted C2group or a metallocene-substituted C2group, 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.

According to the data in Table 6:

When the substituent on the bridging atom in the metallocene compound is a C5-C15group substituted with an amine group or a C5-C15group substituted with a metallocene group, the prepared catalyst has higher catalytic activity for the polymerization of propylene.

According to the data in Tables 1-6:

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.