Metallocene compounds, and methods for their preparation and applications

Abstract

A metallocene compound having a structure represented by formula (I). The group connected to the crosslinking atom of the metallocene compound is an amine-substituted group and / or a metallocene-substituted group and / or a substituted metallocene group. The structure enables a metallocene catalyst containing the metallocene compound to have high catalytic activity and allows for the synthesis of metallocene polypropylene having high isotacticity. (I)

Description

Technology Field

[0001] This application claims priority to the following patent applications filed on October 30, 2019, the entirety of which is incorporated herein by reference:

[0002] 1. Chinese patent application CN201911047955.1, titled "Transition metal catalyst having two asymmetrically cross-linked indenyl groups, method of preparation thereof and uses thereof"; and

[0003] 2. Chinese patent application CN201911046672.5, titled "Silicon-crosslinked metallocene compound, method of preparation thereof and use thereof".

[0004] The present invention relates to metallocene compounds, methods for manufacturing the same, and applications, and in particular to metallocene catalysts containing metallocene compounds, methods for manufacturing the catalyst, and uses. Specifically, the present invention relates to the field of metallocene catalyst technology. Background Technology

[0005] Metallocene polypropylene (mPP) has excellent utility in fibers, injection molding, films, etc., and market demand has been increasing recently. These resin products have high requirements for the stereoregular structure of polypropylene, and the structure of polypropylene is controlled and regulated by the structure of the catalyst.

[0006] Highly isotactic metallocene polypropylenes are important resins. These metallocene polypropylenes are synthesized by controlling the growth of propylene chains through stereoanantiomorphic sites of catalysts. Catalysts capable of controlling chain elongation reactions through stereoanantiomorphic sites need to possess C2-axis or lower C1-axis symmetry (Chem. Rev. 2000, 100, 1223). Compounds of Group IV metals such as titanium, zirconium, or hafnium, as well as cross-linked diendene rings with racemic structures or their derivatives, possess these properties. In the 1980s, Brintzinger's team synthesized racemic ethyl diendene ligands and subsequently synthesized racemic ethyl bis(tetrahydroindene) ligands (J. Organomet. Chem. 1982, 232, 233; 1985, 288, 63). Synthesized titanium and zirconium compounds catalyze propylene under the action of methylaluminoxane (MAO) additives to form polypropylene with a high isotactic structure, whereas catalysts with a mesostructure cannot catalyze propylene to produce polypropylene with high isotacticity. The activity of these racemic catalysts, as well as the molecular weight and isotacticity of the products, are very sensitive to temperature. In the range of -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 100 times, and the difference between the highest average molecular weight (300,000 Dalton) and the lowest average molecular weight (12,000 Dalton) is 25 times, whereas the molecular weight distribution of the polymer does not change significantly in the range of 1.9 to 2.6, and the isotacticity [mmmm] changes within the range of 86.0-91.0 (Angew. Chem. Int. Ed. Engl. 1985, 24, 507).In 1989, Herrmann et al. synthesized racemic, silicon-based indenezirconium compounds. Subsequently, Spalec and Herrmann et al. modified the inden ring using substituents. Polypropylene prepared catalytically under the action of MAO at higher temperatures reaches or nearly reaches industrial application levels in terms of reactivity, molecular weight, molecular weight distribution, and isotacticity (up to 98%, mp 152°C) (Angew. Chem. Int. Ed. Engl. 1989, 28, 1511; 1992, 31, 1348). Since then, a series of cross-linked non-indene cyclic group IV metallocene catalysts and their derivative systems have been successively developed and used for the isotactic and catalytic polymerization of propylene (Chem. Rev. 2000, 100, 1253).

[0007] Although reaction conditions such as temperature, pressure, time, and catalyst concentration, solvents, auxiliaries, impurity scavengers, hydrogen molecule regulators, and other factors have a significant impact on the catalytic reaction for producing highly isotactic polypropylene, the control and regulation of stereomantoid sites in the racemic structure play an essential and decisive role. These structural features are primarily reflected in the following five aspects: the inden ring, substituents of the inden ring, bridging groups, a central metal, and groups bonded to the central metal that can initiate chain growth. Those skilled in the art are well aware that innovation in any one of these five aspects may patent the present invention.

[0008] The present invention focuses primarily on the important role of the crosslinker. The crosslinker S' is referred to in earlier U.S. patents US5017714 and US5120867 as a silicon-containing crosslinker of 1 to 4 atoms selected from silanilene, silaalkylene, oxasilanylene, and oxasilaalkylene. Subsequently, patent US5145819 describes a crosslinking structure group -(CR 8 R 9 ) m -R 7 -(CR8 R 9 ) n It provides extensive definition and patent protection for -, where R above 7 is M 2 (R 11 )(R 12 )-, -M 2 (R 11 )(R 12 )-M 2 (R 11 )(R 12 )-, -M 2 (R 11 )(R 12 )-(CR2 13 )-, -OM 2 (R 11 )(R 12 )-O-, -C(R 11 )(R 12 )-, -OM 2 (R 11 )(R 12 )-, =BR 11 , =AlR 11 , -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR 11 , =CO, =PR 11 or =P(O)R 11 and R 11 , R 12 , R 13 It may be the same or different and hydrogen, halogen atoms, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C6-C 10 Aryl, C6-C 10 Fluoroaryl, C1-C 10 Alkoxy, C2-C 10 alkenyl group, C7-C 40 It can be an arylalkyl group, and R 11 and R 12 and R 11 and R 13 They are connected to each other through atoms to form a ring; M 2 is Si, Ge, or Sn; R 8 and R 9 It may be the same or different, and R11 It is defined in the same way as; m and n may be the same or different, being 0, 1, or 2, or m + n is 0, 1, or 2. In these definitions, R 7 is preferably -C(R 11 )(R 12 )-, -Si(R 11 )(R 12 )-, -Ge(R 11 )(R 12 )-, -O-, -S-, =SO, =PR 11 or =P(O)R 11 It is referred to as. Based on the above disclosure, US5239022 further defines that alkyl refers to a linear or branched alkyl and halogen refers to fluorine, chlorine, bromine, and iodine. US5239022 also defines R 11 , R 12 and R 13 A preferred definition of a crosslinker is provided. For details, refer to the original publications. In patents US5243011, US5276208, US5350817, US5374752, US5483002, US5672668, US5714427, US5741868, US6087291, US6114479, US6124230, US6228795B1, and US2003 / 0088022A1, the definition of a crosslinker is similar to that above. In US5770753, the crosslinker is R, in particular, comprising the following: 13 It is directly defined as: -M 2 (R 14 )(R 15 )-, -M 2 (R 14 )(R 15 )-M 2 (R 14 )(R 15 )-, -C(R 14 )(R 15 )-C(R 14 )(R 15 )-, -OM 2 (R 14 )(R 15 )-O-, -C(R14 )(R 15 )-, -OM 2 (R 14 )(R 15 )-, -C(R 14 )(R 15 )-M 2 (R 14 R 15 )-, -C(R 14 )(R 15 )-C(R 14 R 15 )- C(R 14 )(R 15 )-, =BR 14 、=AlR 14 , -Ge-, -O-, -S-, =SO, =SO2, =NR 14 , =CO, =PR 14 , or =P(O)R 14 , here R 14 and R 15 It may be the same or different, hydrogen, halogen atoms, C1-C 10 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C6-C 10 Aryl, C6-C 10 Fluoroaryl, C6-C 10 phenol group, C2-C 10 Alkenyl, C7-C 40 Arylalkyl, C7-C 40 Alkylaryl, C8-C 40 It is an aryl alkenyl, or R 14 and R 15 are connected to each other through atoms to form one or more rings; M 2is Si, Ge, or Sn. Subsequent patents US5786432, US5380821, US5840644, US5840948, US5852142, US5929264, US5932669, US6051522, US60517272, US6057408, US6242544B1, US6255506B1, US6376407B1, US63764408B1, US63764409B1, US63764410B1, US63764411B1, US63764412B1, US2001 / 0021755A1, US2006 / 016490A1, and US2006 / 0252637A1 all have similar or substantially identical crosslinking structures It represents. In US63764413B1, the crosslinking group is biphenyl M 2 (C6R 17 R 18 R 19 R 20 -C6R 21 R 22 R 23 R 24 Defined as )-, and R 17 to R 24 The overall definition of is R 1 and R 2 Designated as, or R 20 and R 21 including, Two or more adjacent radicals R 17 to R 24 They are connected to each other through atoms to form one or more rings, and R 17 to R 24 is preferably H. R 1 and R 2 They may be identical or different. These are H, C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 10 Aryl, C6-C 10 Phenol, C2-C 10 Alkenyl, C7-C 40 Arylalkyl, C7-C 40 Alkylaryl, C8-C 40It is one of an aryl alkenyl, OH, a halogen atom, or a conjugated diene (randomly substituted with one or more hydrocarbyl groups), a 3-carbon hydrogen silicon group or a 3-carbon hydrogen group, or a 3-carbon hydrogen silicon-substituted hydrocarbyl group (wherein the number of non-hydrogen atoms is up to 30). These patents include US5616747, US6376627B1, US6380120B1, US6380121B1, US6380122B1, US6380123B1, US6380124B1, US6380130B1, US6380130B1, US6380134B1, etc. Patents US5391790 and US5616747 are -[M 2 (R 8 )(R 9 )] p -R defined as 6 - directly represents the bridging group with, above, M 2 is C, Si, Ge, or Sn; R 8 and R 9 It may be the same or different, and H, C1-C 20 Alkyl, C6-C 14 Aryl, C1-C 10 Alkoxy, C2-C 10 Alkenyl, C7-C 20 Arylalkyl, C7-C 20 Alkylaryl, C6-C 10 Phenol, C1-C 10 Fluoroalkyl, C6-C 10 Haloaryl, C2-C 10 Alkynyl, -SiR 7 Referred to as a 3, halogen, or pentagonal or hexavalent heteroaromatic radical (containing one or more heteroatoms), connected through atom(s) to form one or more rings; p is 1, 2, or 3. US5739366 defines a crosslinking group Y, which is a divalent C1-C 20 Hydrocarbyl group, divalent C1-C 20Hydrocarbyl halides, divalent silicon-containing groups, divalent germanium-containing groups, and divalent tin-containing groups, -O-, -CO-, -S-, -SO-, -SO2-, -NR 5 -, -P(R 5 )-, -P(O)(R 5 )-, -BR 5 - or -AlR 5 - (R 5 is H, a halogen atom, C1-C 20 Hydrocarbyl group, divalent C1-C 20 It is referred to as a halogenated hydrocarbyl group. In US6218558, US6252097B1, and US6255515B1 filed by Japan Polymer Chemical Company, the benzene ring of the indene ring is extended into a hepta-membered ring, and the corresponding crosslinking group Q is a divalent C1-C 20 Hydrocarbyl group, divalent C1-C 20 Halogenated group, C1-C 20 Hydrocarbyl group or C1-C 20 Silylene containing a halogenated hydrocarbyl group, C1-C 20 Hydrocarbyl group or C1-C 20 Oligosyllenyl groups containing halogenated hydrocarbyl groups, or C1-C 20 Hydrocarbyl group or C1-C 20 It is a germanenyl group containing a halogenated hydrocarbyl group, connected by two five-membered rings. In US6444606B1, US7342078B2, and US2003 / 0149199A1, the crosslinking group R 9 is -OM 2 (R 10 )(R 11 )-O-, -C(R 10 )(R 11 )-, -OM 2 (R 10 )(R 11 )-, -C(R 10 )(R 11 )-M 2 (R 10 R 11 )-, -M2 (R 10 )(R 11 )-, -M 2 (R 10 )(R 11 )-M 2 (R 10 )(R 11 )-, -C(R 10 )(R 11 )-C(R 10 )(R 11 )-, -M 2 (R 10 )(R 11 )-[C(R 10 R 11 )] x -M 2 (R 10 )(R 11 )-, -C(R 10 )(R 11 )-C(R 10 R 11 )-C(R 10 )(R 11 )-, >BR 10 , >AlR 10 , -Ga-, -O-, -S-, >SO, >SO2, >NR 10 , >CO, >PR 10 , >P(O)R 10 or >R(O)R 10 It is defined as, where R above 10 and R 11 It may be the same or different and consists of hydrogen, halogen atoms, or C1-C 40 For example, C1-C 20 Alkyl, C1-C 10 Fluoroalkyl, C1-C 10 Alkoxy, C6-C 14 Aryl, C6-C 10 Fluoroaryl, C6-C 10 Phenol, C2-C 10 Alkenyl, C7-C 40 Arylalkyl, C7-C 40 Alkylaryl, C8-C 40 It is an aryl alkenyl, or R 10 and R 11They are connected to each other through atoms and form one or more rings; M 2 is Si, Ge, or Sn.

[0009] The crosslinking group is connected to two cyclopentadienyl, indenyl, or fluorenyl groups. That is, the two groups are stereo-defined. Such crosslinking increases the rigidity of the ligand structure and plays an important role in the formation of a racemic structure, which is a characteristic of the catalyst. Catalysts with a racemic structure can effectively regulate and control the chain growth of stereoremote sites of propylene, thereby enabling the production of metallocene polypropylene with high isotacticity.

[0010] Although many cross-linked metallocene catalysts have been reported, few of them have industrial applications or potential for application. This is because industrial applications place high requirements on the isotacticity of metallocene polypropylene. For example, metallocene polypropylene produced by some companies can be used in resin products only if its isotacticity [mmmm] is 97% or higher. Polypropylene products in China are generally produced using traditional Natta-type catalysts. Some of these catalysts are added along with simple metallocene compound components. In this regard, there are few reports on the use of metallocene compounds as catalysts due to theoretical and technical difficulties.

[0011] Polypropylene products in China are basically produced using traditional supported Ziegler-Natta catalysts. Because there are still technical difficulties in this regard, there are few reports on the use of cross-linked two-group metallocene catalysts to control the production of polypropylene with high isotacticity. The problem to be solved

[0012] The first technical problem that the present invention aims to solve is that conventional metallocene catalysts do not have sufficiently high activity to provide new metallocene compounds (metallocene compounds in which a group connected to a bridge atom of a metallocene compound is substituted with an amino group, and / or a group substituted with a metallocene group and / or a substituted metallocene group). A special structure imparts high catalytic activity to a metallocene catalyst containing a metallocene compound; additionally, metallocene polypropylene with high regularity can be synthesized using the metallocene catalyst.

[0013] The second technical problem that the present invention aims to solve is to provide a method for manufacturing a metallocene compound to solve the first technical problem.

[0014] The third technical problem that the present invention aims to solve is to provide a metallocene catalyst employing a metallocene compound to solve the first technical problem.

[0015] The fourth technical problem that the present invention aims to solve is to provide a method for manufacturing a catalyst to solve the third technical problem.

[0016] The fifth technical problem that the present invention aims to solve is to provide a use for the metallocene compound of the first technical problem or a catalyst for solving the third technical problem. means of solving the problem

[0017] To solve the above-mentioned first technical problem, the technical solution means adopted in the present invention is as follows:

[0018] A metallocene compound having a structure represented by the following formula (I) is provided:

[0019]

[0020] Equation (I)

[0021] In Equation (I), R I and RII is the same or different, and R I and R II At least one of them is an amino-substituted C1-C 20 Hydrocarbyl, amino-substituted C1-C 20 Halohydrocarbyl, amino-substituted C1-C 20 Alkoxy, and amino-substituted C6-C 20 Selected from phenolic groups; and / or R I and R II At least one of them is a metallocene-substituted C1-C 20 Hydrocarbyl, metallocene-substituted C1-C 20 Halohydrocarbyl, metallocene-substituted C1-C 20 Alkoxy and metallocene-substituted C6-C 20 Selected from phenolic groups; and / or R I and R II At least one of them is C1-C 20 Hydrocarbyl, C1-C 20 Halohydrocarbyl, C1-C 20 Alkoxy or C6-C 20 Selected from metallocene groups substituted with phenolic groups;

[0022] Z is selected from carbon, silicon, germanium, and tin;

[0023] Cp III As shown in Formula (II), is a cyclopentadienyl containing or not containing a substituent, an indenyl containing or not containing a substituent, or a fluorenyl containing or not containing a substituent, and R i , R ii , and R iii is a substituent within the corresponding ring;

[0024]

[0025] Formula (II)

[0026] R i , R ii and R iiiLinear or branched saturated or unsaturated C1-C atoms that are identical or different and each independently contain or do not contain hydrogen and heteroatoms. 20 It is hydrocarbil;

[0027] E is NR iv or PR iv And;

[0028] R iv is a linear or branched saturated or unsaturated C1-C that contains or does not contain hydrogen and heteroatoms. 20 Selected from hydrocarbil;

[0029] M is selected from group IVB metals;

[0030] L IV and L V are linear or branched saturated or unsaturated C1-C atoms that are identical or different and each independently contain or do not contain hydrogen and heteroatoms. 20 It is hydrocarbyl; and

[0031] n is 1 or 2.

[0032] According to the present invention, when n is 1, Cp III is any one of the above cyclopentadienyl, indenyl, or fluorenyl; and when n is 2, Cp III is 2 of the above cyclopentadienyls, 2 of the above indenyls, or 2 of the above fluorenyls, or Cp III is 2 of the above cyclopentadienyl, indenyl, or fluorenyl. When n is 2, two Cp III The energy may be the same or different.

[0033] According to a preferred embodiment of the present invention, the amino is as shown in the following formula (III):

[0034]

[0035] Equation (III)

[0036] In Equation (III), Ra and R b are identical or different, and each independently hydrogen, C1-C6 alkyl, C6-C 18 Aryl, C7-C 20 Arylalkyl, and C7-C 20 Alkylaryl, preferably C1-C6 alkyl, C6-C 12 Aryl, and C7-C 10 Arylalkyl is selected from C1-C4 alkyl, more preferably C1-C4 alkyl, phenyl, and C7-C9 arylalkyl.

[0037] According to a preferred embodiment of the present invention, the metal of the metallocene group is Fe, and preferably, the metallocene group is ferrocenyl.

[0038] According to a preferred embodiment of the present invention, in the above formula (I), R I and R II is the same or different, and R I and R II At least one of them is an amino-substituted C1-C 10 Hydrocarbyl, amino-substituted C1-C 10 Halohydrocarbyl, amino-substituted C1-C 10 Alkoxy, and amino-substituted C6-C 10 Selected from phenolic groups; and / or R I and R II At least one of them is a metallocene-substituted C1-C 10 Hydrocarbyl, metallocene-substituted C1-C 10 Halohydrocarbyl, metallocene-substituted C1-C 10 Alkoxy and metallocene-substituted C6-C 10 Selected from phenolic groups; and / or R I and R II At least one of them is C1-C 10 Hydrocarbyl, C1-C 10 Halohydrocarbyl, C1-C 10 Alkoxy or C6-C 10 It is selected from metallocene groups substituted with phenolic groups.

[0039] According to a preferred embodiment of the present invention, in the above formula (I), R I and R II is the same or different, and R I and R II At least one of the is selected from amino-substituted C1-C6 hydrocarbyl, amino-substituted C1-C6 halohydrocarbyl, amino-substituted C1-C6 alkoxy, and amino-substituted C6-C8 phenolic groups; and / or R I and R II At least one of the is selected from metallocene-substituted C1-C6 hydrocarbyl, metallocene-substituted C1-C6 halohydrocarbyl, metallocene-substituted C1-C6 alkoxy, and metallocene-substituted C6-C8 phenolic groups; and / or R I and R II At least one of the following is selected from metallocene groups substituted with C1-C6 hydrocarbyl, C1-C6 halohydrocarbyl, C1-C6 alkoxy, or C6-C8 phenolic groups.

[0040] According to a preferred embodiment of the present invention, in the above formula (I), R I and R II is the same or different, and R I and R II At least one of the is selected from amino-substituted C1-C6 hydrocarbyls; and / or R I and R II At least one of the is selected from metallocene-substituted C1-C6 hydrocarbyls; and / or R I and R II At least one of them is selected from metallocene groups substituted with C1-C6 hydrocarbyl.

[0041] According to a preferred embodiment of the present invention, in the above formula (I), R I and R II is the same or different, and R I and R II At least one of the is selected from amino-substituted C1-C6 linear alkyls; and / or R I and RII At least one of the is selected from metallocene-substituted C1-C6 linear alkyls; and / or R I and R II At least one of them is selected from metallocene groups substituted with C1-C6 linear alkyls.

[0042] According to a preferred embodiment of the present invention, in the above formula (I), R I and R II is the same or different, and R I and R II At least one of the is selected from amino-substituted C1-C4 linear alkyls; and / or R I and R II At least one of the is selected from C1-C4 linear alkyls substituted with metallocene groups; and / or R I and R II At least one of them is selected from metallocene groups substituted by C1-C4 linear alkyl groups.

[0043] According to a preferred embodiment of the present invention, R I and R II If one of the units is selected from the units defined above, the other unit is C1-C 20 Halohydrocarbyl, C1-C 20 Alkoxy and C6-C 20 It can be selected from phenolic groups, preferably C1-C 10 Hydrocarbyl, C1-C 10 Halohydrocarbyl, C1-C 10 Alkoxy and C6-C 10 It can be selected from phenolic groups, more preferably from C1-C6 hydrocarbyl, C1-C6 halohydrocarbyl, C1-C6 alkoxy, and C6-C8 phenolic groups, and more preferably from C1-C6 hydrocarbyl.

[0044] According to the present invention, R i , R ii , and R iii represents the corresponding cyclic substituent in the above chemical formula. CpII If α is a cyclopentadienyl group, 1 or up to 4 Rs i can be independently connected to the cyclopentadienyl group at any one, two, three, or four positions (without selection) of the cyclopentadienyl group; Cp III If α is an indenyl group, 1 or 2 R's i It can be independently connected to the indenyl group at one or both of the two positions of the five-membered ring without selection; and 1 to 4 R ii can be independently connected to the indenyl group at 1, 2, 3, or all 4 positions (without selection) of the 4 positions of the 6-membered ring; R iii If the benzene ring containing is part of an indenyl ring, R iii The definition of is R ii Same as; Cp III When this is a fluorenyl group, 1 to 4 R ii and 1 to 4 R iii Each of the 6-membered rings can be independently connected at any 1, 2, 3, or 4 positions of the two 6-membered rings. R i , R ii , and R iii Each is independently hydrogen, linear, or branched C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkylaryl, or C7-C 20 Representing arylalkyl groups, these groups optionally contain one or more heteroatoms and may be saturated or unsaturated. R i , R ii , and R iii It can form saturated or unsaturated cyclic groups, and these groups may optionally contain one or more heteroatoms.

[0045] According to a preferred embodiment of the present invention, in formula (II), R i , Rii and R iii are identical or different, and each independently hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 Haloalkyl, C6-C 20 Aryl, C6-C 20 Haloaryl, C7-C 40 Arylalkyl, C7-C 40 Alkylaryl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C2-C 20 Alkenyl, C2-C 20 alkynyl, C1-C 20 Alkoxy, C6-C 20 phenolic group, C1-C 20 It is selected from aminos and groups containing heteroatoms selected from groups 13 to 17.

[0046] According to a preferred embodiment of the present invention, R in the above formula (II) i , R ii and R iii are identical or different, and each independently hydrogen, C1-C 10 Hydrocarbyl, C1-C 10 Haloalkyl, C6-C 10 Aryl, C6-C 10 Haloaryl, C7-C 20 Arylalkyl, C7-C 20 Alkylaryl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C2-C 10 Alkenyl, C2-C 10 alkynyl, C1-C 10 Alkoxy, C6-C 10 phenolic group, C1-C 10 It is selected from amino groups and groups containing heteroatoms selected from groups 13 to 17.

[0047] According to a preferred embodiment of the present invention, in the above formula (II), R i , R ii and R iiiare identical or different, and each independently hydrogen, C1-C6 hydrocarbyl, C1-C6 haloalkyl, C6-C6 aryl, C6-C6 haloaryl, C7-C 10 Arylalkyl, C7-C 10 It is selected from alkylaryl, C3-C6 cycloalkyl, C3-C6 heterocycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C6-C6 phenolic group, C1-C6 amino, and groups containing heteroatoms selected from groups 13 to 17.

[0048] According to a preferred embodiment of the present invention, in formula (I), R is hydrogen, and linear or branched saturated or unsaturated C1-C, with or without heteroatoms. 10 It is selected from hydrocarbyl.

[0049] According to a preferred embodiment of the present invention, in formula (I), R iv It is selected from linear or branched saturated or unsaturated C1-C6 hydrocarbyl, which may or may not contain hydrogen and heteroatoms.

[0050] According to a preferred embodiment of the present invention, in the formula (I), M is selected from Ti, Zr, and Hf.

[0051] According to a preferred embodiment of the present invention, in the above formula (I), M is Zr.

[0052] According to a preferred embodiment of the present invention, L IV and L V It is identical and is selected from hydrogen, chlorine, methyl, phenyl, benzyl, and dimethylamino.

[0053] To solve the above-mentioned second technical problem, the present invention adopts any of the following technical solution means:

[0054] Option 1:

[0055] The method for manufacturing a metallocene compound as described above is

[0056] When n is 2, the manufacturing method includes the following:

[0057] S1. H2(Cp III React ) with an alkali metal-organic compound to obtain the corresponding [H(Cp III )] - Step of forming an alkali metal salt;

[0058] S2. [H(Cp III )] - Alkali metal salts R I R II React with ZX2 to R I R II Z[H(Cp III Step of forming )]2;

[0059] S3. R I R II Z[H(Cp III React )]2 with an alkali metal-organic compound to obtain the corresponding R I R II Z(Cp III )2 2- Step of forming an alkali metal salt;

[0060] S4. R I R II Z(Cp III )2 2- 2 ml of alkali metal salt IV L V By reacting with to cause a salt removal reaction, R I R II Z(Cp III )2ML IV L V Step of obtaining;

[0061] When n is 1, the manufacturing method includes the following:

[0062] S1. H2(Cp III ) and H2(E) are each reacted with an alkali metal-organic compound to obtain the corresponding [H(Cp III )] - Alkali metal salts and corresponding [H(E)] - Step of forming an alkali metal salt;

[0063] S2. [H(Cp III )] - Alkali metal salts and [H(E)] - Alkali metal salts R I R II React with ZX2 to R I R II Z[H(Cp III Step of forming )] [H(E)];

[0064] S3. R I R II Z[H(Cp III React [H(E)] with an alkali metal-organic compound to obtain the corresponding R I R II Z(Cp III )(E) 2- Step of forming an alkali metal salt;

[0065] S4. R I R II Z(Cp III )(E) 2- 2 ml of alkali metal salt IV L V By reacting with to cause a salt removal reaction, R I R II ZCp III EML IV L V Step of obtaining;

[0066] In the above, X is selected from Cl, Br, and I;

[0067] Preferably, in S4, R I R II Z(Cp III )2 2- Alkali metal salt or R I R II Z(Cp III )(E) 2- Alkali metal salts are directly x2 ml without separation. IV L V It reacts with to cause a salt removal reaction.

[0068] Option 2:

[0069] The method for manufacturing a metallocene compound as described above is

[0070] Precursor R I HZ(Cp III ) n (E) 2-n ML IV L V and R II The method includes the step of preparing a metallocene compound by performing a Z hydrogenation reaction between precursors;

[0071] R above II The precursor is a molecule containing multiple bonds, preferably, said molecule containing multiple bonds is selected from organic multiple bond molecules, CO and CO2, and said multiple bonds are selected from group 13 to 16 elements of the same or different atoms, or preferably one or more of C=C, C≡C, C=N, C≡N, C=O, C≡P, N=N, C=S, C=C=C, C=C=N, C=C=O, and N=C=N.

[0072] According to the present invention, the metallocene compound can be prepared by both Option 1 and Option 2.

[0073] According to a preferred embodiment of the present invention, the aforementioned metallocene compound is prepared by Option 2. That is, the metallocene compound is precursor R I HZ(Cp III ) n (E) 2-n ML IV L V , R II HZ(Cp III ) n (E) 2-n ML IV L V or H2Z(Cp III ) n (E) 2-n ML IV L Vand are prepared by the addition reaction of molecules containing multiple bonds of ZH. Collins reported the stepwise synthesis of MeHZ(Cp)2Zr(NMe2)2 and MeHZ(Ind)2Zr(NMe2)2 (Macromolecules 2001, 34, 3120), namely, preparing the dimeric ligands MeHZ(CpH)2 and MeHZ(IndH)2, respectively, and then reacting them with Zr(NMe2)4 to produce MeHZ(Cp)2Zr(NMe2)2 and MeHZ(Ind)2Zr(NMe2)2. This method is similar to conventional synthetic methods for removing protons from metallocene rings or non-metallocene compounds. The two compounds were reacted with an excess of Me3ZCl to obtain MeHZ(Cp)2ZrCl2 and MeHZ(Ind)2ZrCl2 compounds.

[0074] Precursor R I HZ(Cp III ) n (E) 2-n ML IV L V , R II HZ(Cp III ) n (E) 2-n ML IV L V or H2Z(Cp III ) n (E) 2-n ML IV L V For the manufacture of [the product], the technical solution adopted in the present invention may use this method or the salt removal method as mentioned in the background art, but the one-pot method is preferred. The present invention provides a specific implementation of the one-pot method, and the implementation process of the one-pot method does not change when the selected raw material is changed.

[0075] When n is 2, R I HZX2 is 2 moles of H(Cp III ) is selected to react with alkali metal salts (H(Cp III When ) is two different groups, each is 1 mole). H(Cp III) Alkali metal salts are ligands H2(Cp III ) is prepared by reacting an equivalent of an alkali metal-organic compound. The alkali metal-organic compound is selected from the group consisting of metal hydrides, metal alkyls, alkenyl metals, aryl metals, and amine metals, preferably a metal alkyl; the alkali metal is selected from Li, Na, and K, preferably Li; and X is selected from Cl, Br, and I, preferably Cl. The resulting R I HZ[H(Cp III )]2 does not need to be separated and is used directly in the next reaction. There are two reaction equations as follows.

[0076] a) R I HZ[H(Cp III )]2 is the stable small molecule HL viii or HL viv To remove L viii L viv ML IV L V Reacting with R I HZ(Cp III )2ML IV L V Get , L viii and L viv is a leaving group selected from hydrogen, alkyl, aryl, and amine, which may be the same or different. Preferably, L viii and L viv It is identical and selected from methyl, phenyl, and dimethylamino groups.

[0077] b) R I HZ[H(Cp III )]2 reacts with 2 moles of an alkali metal-organic compound to form an alkali metal salt, where the definition of the alkali metal-organic compound is the same as above; then, X2 ml of the alkali metal salt is used for salt removal. IV L V react with salt R I HZ(Cp III )2ML IV LV We obtain, where X has the same definition as above.

[0078] When n is 1, R I HZX2 is 1 mole of H(C pIII ) is selected to react with an alkali metal salt and 1 mole of H(E) alkali metal salt. H(Cp III The preparation of alkali metal salts is identical to the preparation of H(E). Alkali metal salts are prepared by reacting H2(E) with an equal amount of an alkali metal-organic compound, and the definition of the alkali metal-organic compound is as stated above. The resulting R I HZ[H(Cp III )][H(E)] does not need to be separated and is used directly in the following reaction. There are the following two reaction equations.

[0079] a) R I HZ[H(Cp III )][H(E)] is the stable small molecule HL viii or HL viv To remove L viii L viv ML IV L V R reacts with V I HZ(Cp III )(E)ML IV L V We get, and here L viii and L viv is as defined above.

[0080] b) R I HZ[H(Cp III )][H(E)] reacts with 2 moles of an alkali metal-organic compound to form an alkali metal salt, where the definition of the alkali metal-organic compound is the same as above; then, 2 ml of the alkali metal salt is used for salt removal. IV L V react with salt R I HZ(Cp III )2ML IV L V We obtain, where X has the same definition as above.

[0081] R II HZ(Cp III ) n (E) 2-n ML IV L V R to manufacture II Select HZX2 or H2Z(Cp III ) n (E) 2-n ML IV L V Selecting H2ZX2 to manufacture is similar to the reaction equation above.

[0082] R I HZ(Cp III ) n (E) 2-n ML IV L V , R II HZ(Cp III ) n (E) 2-n ML IV L V or H2Z(Cp III ) n (E) 2-n ML IV L V During the preparation of, the reaction is carried out in an aprotic solvent. The solvent is selected from linear or branched alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, ether compounds, and cyclic ether compounds, and preferably selected from toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether, and dioxane. Among these, H2(Cp III ), H2(E), R I HZ[H(Cp III )]2, R II HZ[H(Cp III )]2, H2Z[H(Cp III )]2, R I HZ[H(Cp III )][H(E)], R II HZ[H(Cp III)][H(E)] or H2Z[H(Cp III )][H(E)] is reacted with an alkali metal-organic compound at a temperature of -60 to 140°C, the preferred temperature range being -20 to 110°C; the reaction time is greater than 0.016h, and the preferred reaction time range is 2 to 100h. R I HZX2, R II HZX2, H2ZX2with H(Cp III ) or H(E) reaction of alkali metal salts, X2ML IV L V and the reaction of RIHZ[(CpIII)]2, RIIHZ[(CpIII)]2, H2Z[(CpIII)] 2, RIHZ[(CpIII)][(E)], RIIHZ[(CpIII)][(E)] or R I HZ[(Cp III )]2, R II HZ[(Cp III )]2, H2Z[(Cp III )]2, R I HZ[(Cp III )][(E)], R II HZ[(Cp III )][(E)] or H2Z[(Cp III )][(E)] alkali metal salts are carried out at a temperature of -75 to -100°C, preferably the temperature range is -75 to 60°C; the reaction time is greater than 0.1h, preferably the reaction time range is 6-100h. R for small molecule removal I HZ[H(Cp III )]2, R II HZ[H(Cp III )]2, H2Z[H(Cp III )]2, R I HZ[H(Cp III )][H(E)], R II HZ[H(Cp III )][H(E)], or H2Z[H(Cp III )][H(E)] and L viii L viv ML IV L VThe reaction is carried out at a temperature of 0 to 160°C, with a preferred temperature range of 20 to 140°C; the reaction time is greater than 0.1h, and preferably the reaction time is in the range of 2 to 100h.

[0083] The technical solution further provided by the present invention is precursor R I HZ(Cp III ) n (E) 2-n ML IV L V , R II HZ(Cp III ) n (E) 2-n ML IV L V or H2Z(Cp III ) n (E) 2-n ML IV L V (I) is prepared by a ZH addition reaction between molecules containing multiple bonds. In the molecules containing multiple bonds, the multiple bonds are selected from elements of groups 13 to 16, which may be atoms of the same type or different types, and preferably may be 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 participation of a catalyst is required in the ZH addition reaction. The catalyst is selected from transition metal catalysts and Lewis acid catalysts, preferably platinum catalysts of transition metal catalysts and B(C6F5)3 catalysts of Lewis acids. To better achieve the object of the present invention, preferably L in the aforementioned precursor IV and L V A catalyst is required that does not affect or affect the reaction of ZH and multiple bonds. This means that the catalyst L in the aforementioned precursor IV and L V When L interacts with and influences the addition reaction of ZH having multiple bonds IV and L VThis means that it must undergo a group conversion reaction through the related compound from which the group was prepared. This results in a conversion to a group that does not affect the reaction between the multiple bond and ZH. For example, L IV and L V When γ is methyl, the B(C6F5)3 catalyst forms a complex with methyl to form [MeB(C6F5)3] - Since it forms, the catalytic effect is lost. Afterwards, L IV and L V It must be converted to NMe2 or other non-reacting groups.

[0084] Precursor R I HZ(Cp III ) n (E) 2-n ML IV L V , R II HZ(Cp III ) n (E) 2-n ML IV L V or H2Z(Cp III ) n (E) 2-n ML IV L VThe reaction of ZH with a molecule containing multiple bonds is carried out in a protic solvent. The solvent may be selected from linear or branched alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, ethers, and cyclic ethers, and preferably from toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ethers, and dioxanes. 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, with a preferred temperature range of 0 to 90°C; the reaction time is greater than 0.1h, and the reaction time is preferably in the range of 2-50h. The target product (I) is separated or purified by recrystallization.

[0085] According to the present invention, "Z" is preferably silicon.

[0086] According to a preferred embodiment of the present invention, the Z hydrogenation reaction is carried out in the presence of a catalyst selected from a transition metal catalyst and a Lewis acid catalyst, preferably a platinum catalyst of the transition metal catalyst and B(C6F5)3 of the Lewis acid catalyst.

[0087] According to a preferred embodiment of the present invention, the amount of catalyst used in the Z hydrogenation reaction is 0.00001 to 50% of the total mass of the reactants, preferably 0.01 to 20%.

[0088] According to a preferred embodiment of the present invention, the temperature of the Z hydrogenation reaction is -30 to 140°C, preferably 0 to 90°C.

[0089] According to a preferred embodiment of the present invention, the reaction time of the Z hydrogenation reaction is greater than 0.1h, preferably 2-50h.

[0090] According to a preferred embodiment of the present invention, the obtained precursor is separated or purified by recrystallization, and the solvent for recrystallization is an aprotic solvent; preferably selected from linear or branched alkanes and cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, ethers and cyclic ethers; more preferably selected from toluene, xylene, hexane, heptane, cyclohexane and methylcyclohexane.

[0091] According to a preferred embodiment of the present invention, precursor R I HZ(Cp III ) n (E) 2-n ML IV L V It is manufactured by a one-pot method of chemical reaction.

[0092] According to a preferred embodiment of the present invention, when n is 2, precursor R I HZ(Cp III ) n (E) 2-n ML IV L V The method of manufacturing includes the following:

[0093] Step 1) H2(Cp III React ) with an alkali metal-organic compound to obtain the corresponding [H(Cp III )] - Step of forming an alkali metal salt;

[0094] Step 2) [H(Cp III )] - Alkali metal salts R I React with HZX2 to R I HZ[H(Cp III Step of forming )]2;

[0095] Step 3) R I HZ[H(Cp III )]2 without separation L viii L viv ML IV L Vstable small molecule L by direct reaction with viii or L viv By removing precursor R I HZ(Cp III )2ML IV L V A step of obtaining; and / or

[0096] R I HZ[H(Cp III A step of forming an alkali metal salt by directly reacting )]2 with an alkali metal-organic compound without separation; x2 mL of the obtained alkali metal salt IV L V React with to cause a salt removal reaction, thereby producing precursor R I HZ(Cp III )2ML IV L V A step of obtaining; and

[0097] When n is 1, precursor R I HZ(Cp III ) n (E) 2-n ML IV L V The method of manufacturing includes the following:

[0098] Step 1) H2(Cp III ) and H2(E) are each reacted with an alkali metal-organic compound to obtain the corresponding [H(Cp III )] - Alkali metal salts and corresponding [[H(E)] - Step of forming an alkali metal salt;

[0099] Step 2) [H(Cp III )] - Alkali metal salts and [H(E)] - Alkali metal salts R I React with HZX2 to R I HZ[H(Cp III Step of forming )][H(E)];

[0100] Step 3) R I HZ[H(Cp III )][H(E)] without separation L viii Lviv ML IV L V stable small molecule L by direct reaction with viii or L viv By removing precursor R I HZCp III EML IV L V A step of obtaining; and / or,

[0101] R without separation I HZ[H(Cp III A step of forming an alkali metal salt by directly reacting )] [H(E)] with an alkali metal-organic compound; thereafter, x2 mL of the obtained alkali metal salt IV L V By reacting with it to cause a salt removal reaction, R I HZCp III EML IV L V Step of obtaining;

[0102] In the above, X is selected from Cl, Br, and I.

[0103] According to the present invention, when using the one-pot method, R I silver precursor R II HZ(Cp III ) n (E) 2-n ML IV L V It is formed by the addition reaction of multiple bonds within a molecule containing ZH bonds and multiple bonds, and R II is precursor R I HZ(Cp III ) n (E) 2-n ML IV L V Formed by the addition reaction of multiple bonds of a molecule containing ZH bonds and multiple bonds, or R I and R II Both are precursors of H2Z (Cp III ) n (E) 2-n ML IV L VIt is formed by the addition reaction of multiple bonds within a molecule containing ZH bonds and multiple bonds; the multiple bond molecule is an organic multiple bond molecule, CO or CO2, preferably an organic multiple bond molecule. Thus, R I and R II It may be the same or different.

[0104] According to a preferred embodiment of the present invention, in each step, the reaction temperature of the reaction is -100°C to 140°C, preferably -85°C to 110°C; and / or the reaction time is greater than 0.016h, preferably 2 to 100h.

[0105] According to a preferred embodiment of the present invention, in each step, the reactants are mixed at -100°C to -20°C, preferably -85°C to -10°C, and reacted at 10°C to 50°C, preferably 20°C to 35°C for 1 hour to 100 hours, preferably 5h to 50h.

[0106] According to a preferred embodiment of the present invention, in each step, the reaction is carried out in an aprotic solvent selected from linear or branched alkanes, cycloalkanes, aromatic compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably from toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ethers and dioxanes.

[0107] According to a preferred embodiment of the present invention, the alkali metal-organic compound is selected from hydrogenated metals, alkyl metals, alkenyl metals, aromatic metals, and amine metals, preferably selected from alkyl metals, and more preferably C1-C6 alkyl metals.

[0108] According to a preferred embodiment of the present invention, the alkali metal is selected from Li, Na, and K, and preferably is Li.

[0109] To solve the third technical problem, the present invention adopts the following technical solution means:

[0110] A catalyst for an α-olefin polymerization reaction comprising a metallocene compound as described above or a metallocene compound prepared according to the manufacturing method described above, a co-catalyst, and a carrier.

[0111] According to a preferred embodiment of the present invention, the co-catalyst is selected from one or more of a Lewis acid and an ionic compound containing a Lewis acid or a non-coordinating anion and a Brønsted 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 Lewis acid or a non-coordinating anion and a Brønsted acid cation is selected from a compound containing one to four perfluoroaryl-substituted borate anions.

[0112] According to a preferred embodiment of the present invention, the alkyl aluminum comprises trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum, tri-isoamyl aluminum, tri-n-amyl aluminum, tri-isohexyl aluminum, tri-n-hexyl aluminum, tri-isoheptyl aluminum, tri-n-heptyl aluminum, tri-isooctyl aluminum, tri-n-octyl aluminum, tri-isononyl aluminum, tri-n-nonyl aluminum, tri-isodecyl aluminum, and tri-n-decyl aluminum; and / or the alkyl aluminoxane comprises methyl aluminoxane, ethyl aluminoxane, and butyl-modified aluminoxane; and / or organic borides include trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and tris(2,4,6-trifluorophenyl)borane.

[0113] According to a preferred embodiment of the present invention, the alkyl aluminum comprises trimethyl aluminum and triethyl aluminum.

[0114] According to a preferred embodiment of the present invention, the perfluoroaryl group is selected from perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, and perfluoroalkyl phenyl, and the cation is selected from N,N-dimethylphenylammonium ion, triphenylcarbonium ion, trialkylammonium ion, and triarylammonium ion.

[0115] According to a preferred embodiment of the present invention, the content of the metallocene compound in the catalyst is 0.001 mass% to 10 mass% with respect to the M element, preferably 0.01 mass% to 1 mass%; and / or the molar ratio of the M element to the Al element of the co-catalyst in the metallocene compound is (1-500):1, preferably (50-300):1.

[0116] According to a preferred embodiment of the present invention, the catalyst has an asymmetric structure. The asymmetric structure can be multilayered, which is R in the metallocene compound. I and R II The asymmetry can be enhanced by referring to the asymmetric structure formed by the interaction between the metallocene compound and the additive, or by the loading of the carrier after the interaction between the metallocene compound and the additive.

[0117] The technical solution adopted by the present invention to solve the above-mentioned fourth technical problem is as follows:

[0118] The above-described method for manufacturing a catalyst includes the step of forming a catalyst by combining a metallocene compound, a co-catalyst, and a support under the action of a solvent.

[0119] According to a preferred embodiment of the present invention, the conditions of the combination are that the temperature of the combination is -40°C to 200°C, preferably 40°C to 120°C; and the time of the combination is greater than 0.016h, preferably 2h to 100h.

[0120] According to a preferred embodiment of the present invention, the solvent is selected from linear hydrocarbons, branched hydrocarbons, cyclic saturated hydrocarbons and aromatic hydrocarbons, and preferably selected from toluene, xylene, n-butane, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane and neoheptane.

[0121] According to a preferred embodiment of the present invention, the method for manufacturing the catalyst comprises the following:

[0122] i) a step of mixing a co-catalyst, a carrier, and a solvent to obtain mixture A;

[0123] ii) a step of mixing mixture A with a metallocene compound to obtain mixture B; preferably, a step of first mixing the metallocene compound in a solvent to form a mixture and then mixing it with mixture A;

[0124] iii) A step of separating the solid from mixture B and drying the solid to produce a catalyst.

[0125] According to a preferred embodiment of the present invention, in step i), the carrier is calcined. Preferably, the conditions for the calcination treatment include a calcination temperature of 50°C to 700°C and a calcination time of 0.5h to 240h.

[0126] According to a preferred embodiment of the present invention, mixture A is heated. Preferably, the conditions of the heat treatment include a heating temperature of 30°C to 110°C and a heating time of 0.1h to 100h.

[0127] According to a preferred embodiment of the present invention, in step iii), the conditions of the drying treatment include a drying temperature of 30°C to 110°C and a drying time of 0.1h to 100h.

[0128] According to a preferred embodiment of the present invention, the solid is washed before drying treatment, preferably the solid is washed with a solvent, and more preferably after washing the solvent until the solvent does not contain metal ions.

[0129] The technical solution adopted by the present invention to solve the above-mentioned fifth technical problem is as follows:

[0130] Use of the aforementioned metallocene compound or the metallocene compound prepared according to the aforementioned manufacturing method or the aforementioned catalyst or the catalyst prepared according to the aforementioned manufacturing method in the field of α-olefin polymerization.

[0131] According to a preferred embodiment of the present invention, the polymerization reaction of the α-olefin is carried out in the presence of the metallocene compound described above or a metallocene compound prepared according to the manufacturing method described above or a catalyst prepared according to the manufacturing method described above to obtain a poly-α-olefin.

[0132] According to a preferred embodiment of the present invention, the polymerization reaction is carried out under solvent-free conditions.

[0133] According to a preferred embodiment of the present invention, the 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 0.01h to 60h, preferably 0.1h to 10h.

[0134] According to a preferred embodiment of the present invention, a metallocene catalyst or a 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 1 g of α-olefin.

[0135] According to a preferred embodiment of the present invention, the α-olefin is C2-C 20 α-olefin, preferably C2-C 14 α-olefins, more preferably ethylene, propylene, 1-butene, 1-pentene, -hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tritecene, 1-tetradecene, 1-pentadecene, 1-heptadiene, 1-octadecene and 1-eicocene, preferentially 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tritecene or 1-tetradecene.

[0136] In some specific embodiments of the present invention, the α-olefin is propylene. When the α-olefin is propylene, a bulk polymerization reaction can be performed using propylene and hydrogen as feedstocks (this bulk polymerization reaction can be performed in a tank reactor or a tubular reactor, and can be performed in a batch or continuous manner), and the amount of hydrogen can be 0 to 0.10 g / g propylene, preferably 0.00001 to 0.10 g / g propylene. Additionally, an impurity blocking agent can be used when polymerizing propylene. The impurity blocking agent is a substance commonly used in the field, and the specific dosage can be 0 to 100 mmol / g propylene, preferably 0.001 to 10 mmol / g propylene.

[0137] In some specific embodiments of the present invention, the α-olefin is ethylene. When the α-olefin is ethylene, a gas phase polymerization reaction is performed, and the reaction temperature is 0-200°C, preferably 20-140°C; and / or the reaction time is 0.016-60h, preferably 0.1-20h; and / or the ethylene 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 remover is 0-100 mmol / g ethylene, and / or hydrogen, and the dosage is 0-0.01 g / g ethylene.

[0138] According to some embodiments of the present invention, the impurity remover is selected from alkyl aluminum compounds, aromatic aluminum compounds, aluminoxan compounds, boron hydride compounds, alkyl magnesium compounds, aromatic magnesium compounds, alkyl zinc compounds, aromatic zinc compounds, alkyl lithium compounds, aromatic lithium compounds, alkyl sodium compounds, aromatic sodium compounds, alkyl potassium compounds, and aromatic potassium compounds; preferably, trimethyl aluminum, triethyl aluminum, trimethyl aluminum isobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, methyl aluminoxan, ethyl aluminoxan, isobutyl aluminoxan, and modified aluminoxan, alkyl aluminum halides, dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, dimethyl zinc, diethyl zinc, di-n-butyl zinc, methyl lithium, n-butyl lithium, and tert-butyl lithium.

[0139] In the present invention, the term "hydrocarbyl" may be alkyl, aryl, alkylaryl, arylalkyl, alkynyl, alkenyl, etc.

[0140] In the present invention, "heteroatom" may refer to heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, etc.

[0141] In the present invention, the term "substituted" may refer to substitution by a substituent selected from halogens, non-carbon oxo acid groups and derivatives thereof, and optionally substituted alkyl, aralkyl, and aryl groups. For example, it includes groups substituted by alkyl groups, aryl groups, amino groups, hydroxyl groups, alkoxy groups, carbonyl groups, oxa groups, carboxyl groups, thiamine groups, sulfur oxyacid, halogen groups, and combinations thereof.

[0142] In the present invention, the term "one-pot method" may refer to a continuous multi-stage synthesis reaction performed in the same reactor.

[0143] In the present invention, "Me" means methyl; "Et" means ethyl; "iPr" means isopropyl; "tBu" means tert-butyl; "iBu" means isobutyl; "iPr" means isopropyl; "Ph" means phenyl; "Fc" means CpFe(C5H4); and "Flu" means fluorenyl.

[0144] In the present invention, "Tol" means toluene.

[0145] The beneficial effects of the present invention are at least as follows:

[0146] 1) Since at least one of the two different groups on the crosslinking atoms of the metallocene compound used in the present invention is an amine substituent and / or a metallocene substituent and / or a substituted metallocene group, the formation of a racemic metallocene catalyst can be promoted. When combined with a co-catalyst and a support, chain growth of olefins such as propylene and ethylene controlled by stereomantically enantiomers can be realized to form highly isotactic metallocene polypropylene or metallocene polyethylene.

[0147] 2) The method for preparing a metallocene compound provided in the present invention can effectively perform the transformation of crosslinking atoms and can produce crosslinking metallocene compounds having various structures and compositions. The crosslinking metallocene compound obtained after hydrogenation of the crosslinking atoms combines with a co-catalyst and a support to form a metallocene catalyst with excellent thermal stability and catalytic activity, and can be used in the polymerization of ethylene or propylene and other alpha-olefins. Specific details for implementing the invention

[0148] The present invention will be further illustrated by the following examples.

[0149] In the following examples, unless otherwise specified, the aluminum / zirconium ratio is the molar ratio of aluminum to zirconium.

[0150] In the present invention, unless otherwise specified, the Al / Zr ratio refers to the molar ratio of Al element to Zr element.

[0151] In this invention, "%" means mass percentage unless otherwise specified.

[0152] In the present invention, the formula for calculating polymerization activity is as follows.

[0153] Polymerization activity = Quality of polymerization product / (Polymerization time × Amount of catalyst × Zirconium content).

[0154] A. Preparation of Metallocene Compounds

[0155] [Synthesized Example 1]

[0156] Preparation of a metallocene compound represented by the following Formula 1:

[0157] 40 mmol of 4-phenyl-2-methylindene was weighed and dissolved in 200 mL of Et2O, then cooled to -78°C. To the resulting mixture, 40 mmol of n-butyllithium in a 2.4 M hexane solution was slowly added dropwise over 15 minutes. After the addition was complete, the mixture was naturally heated to room temperature while stirring, and stirred at room temperature for an additional 12 hours to obtain a lithium indenyl compound solution.

[0158] 220 mmol of Me(PhMeNH2CH2CH2C)SiCl2 was weighed, dissolved in 100 mL of n-hexane, and cooled to -78°C. The prepared lithium indenyl compound solution was slowly added dropwise to the resulting mixture over a period of 30 minutes. Subsequently, the mixture was naturally heated to room temperature while stirring, and stirred for an additional 12 hours at room temperature. Insoluble matter was removed by filtration, and the filtrate was passed through a silica gel column to obtain a yellow solution. The solvent was removed to obtain the yellow compound Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H5)2, with a weight of 8.2 mmol and a yield of 41%.

[0159] 25 mmol of Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H5) was weighed and dissolved in 100 mL of THF, then cooled to -78°C. To the resulting mixture, 10 mmol of n-butyllithium in a 2.4 M hexane solution was slowly added dropwise over 15 minutes. The resulting mixture was naturally heated to room temperature while stirring, and stirred at room temperature for an additional 12 hours to obtain a solution of silicon-crosslinked indenyl lithium compounds.

[0160] 5 mmol of ZrCl4 was weighed and added to 100 mL of THF, and the mixture was cooled to -78°C. While stirring, the solution of the silicon-crosslinked indenyl lithium compound prepared above was slowly added dropwise to the resulting mixture over 15 minutes. Subsequently, the resulting mixture was naturally heated to room temperature under stirring and stirred at room temperature for an additional 12 hours. Insoluble matter was removed by filtration, the filtrate was recovered, and the THF solvent in the filtrate was removed. The remaining solid was extracted with 100 mL of toluene. The extract was crystallized at -20°C to obtain the orange-red zirconocene compound [Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2]ZrCl2 as shown in Formula 1, weighed at 1.2 mmol, and the yield was 24%.

[0161] The method for preparing the metallocene compounds of Formulas 2 to 11 was similar to this, except that in the second step, Me(PhMeNH2CH2CH2C)SiCl2 was replaced with Me(PhMeNH2CH2CH2CH2C)SiCl2, Me(Me2NH2CH2CH2CH2C)SiCl2, Me(Me2NH2CH2C)SiCl2, Me(Me2NH2CH2CH2C)SiCl2, Me(NH2Pr2NH2CH2CH2C)SiCl2, Me(iPr2NH2CH2CH2C)SiCl2, Me(iBuMeNH2CH2CH2C)SiCl2, Me(iBuEtNH2CH2CH2C)SiCl2, Me(iPrEtNH2CH2CH2C)SiCl2, and (Me2NH2CH2C)(iBuMeNH2CH2CH2C)SiCl2, respectively, and finally Zirconocene compounds Me(PhMeNH2CH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 2, weighed as 1.0 mmol, yield 20%), Me(Me2NH2CH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 3, weighed as 1.4 mmol, yield 28%), Me(Me2NH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 4, weighed as 1.2 mmol, yield 24%), Me(Me2NH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 5, weighed as 1.0 mmol, yield 20%), Me(NH2Pr2NH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 6, which was weighed as 1.3 mmol, yield 26%), Me(iPr2NH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 7, 1.0 mmol, yield 20%), Me(iBuMeNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 8, weighed as 0.9 mmol, yield 18%), Me(iBuEtNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2(Equation 9, 0.8 mmol (yield 16%), Me(iPrEtNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 10, weighed 0.9 mmol, yield 18%), and (Me2NH2CH2C)(iBuMeNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 11, weighed 0.6 mmol, yield 12%) were obtained, respectively.

[0162] The method for preparing the metallocene compounds of Formulas 12 to 14 was also similar to this, except that in step 2, Me(PhMeNCH2CH2CH2)SiCl2 was replaced with Me[CpFe(C5H4)CH2CH2]SiCl2, Me[CpFe(C5H4)CH2CH2CH2]SiCl2, and Me[CpFe(C5H4)CH2]SiCl2, respectively, and . Finally, zirconocene compounds Me[CpFe(C5H4)CH2CH2]Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 12, weighed as 1.0 mmol, yield 20%), Me[CpFe(C5H4)CH2CH2CH2]Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 13, weighed as 1.3 mmol, yield 26%), and Me[CpFe(C5H4)CH2]Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 14, weighed as 0.8 mmol, yield 16%) were obtained.

[0163] The method for preparing the metallocene compound of Formula 15 was similar except that in step 1, 4-phenyl-2-methyldenyl was replaced with 4-(4-tert-butyl)phenyl-2-methyldenyl, and in step 2, Me(PhMeNCH2CH2CH2)SiCl2 was replaced with Me[CpFe(C5H4)CH2CH2]SiCl2, and finally, the zirconocene compound Me[CpFe(C5H4)CH2CH2]Si(4-(4-tBuC6H4)-2-MeC9H4)2ZrCl2 (Formula 15, weighed as 1.0 mmol, yield 20%) was obtained.

[0164] [Synthesization Example 2-12 Preparation of Precursor]

[0165] Hydrogen silicon cross-linked bisdenyl zirconocene compound MeHSi(2-Me-7-p-tBuC6 H 4 C 9 H 4 ) 2 ZrCl 2 Manufacturing of (MS-1)

[0166] 2-methyl-7-p-tert-butylphenylindene (5.24 g, 20 mmol) was weighed and dissolved in Tol (80 mL) solvent. N-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise to the mixture at -78°C, and after slowly raising the temperature to room temperature, the mixture was reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly added dropwise to the mixture at -78°C, and after slowly raising the temperature to room temperature, the mixture was stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was left at -78°C, and n-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise to the mixture. After raising the temperature to room temperature, the mixture was stirred continuously for 2 hours to obtain a cloudy orange-yellow solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was placed into a vial. Then, 40 mL of toluene was added to the above-mentioned turbid yellow liquid under nitrogen protection at room temperature. Soon, the color gradually darkened from orange-yellow to brown-black. The reaction was carried out for 1 day. The reaction solution was filtered under nitrogen protection, and the obtained filtrate was desolvated, washed with n-hexane, filtered, and discharged to obtain a yellow solid. The yellow solid was subjected to multi-step recrystallization from toluene at -20°C to obtain 1.76 g (24.2%) of the racemic compound rac-MS-1 and 3.42 g (47.0%) of the meso-MS-1 compound.

[0167] The two compounds were isomers and had the same elemental composition. One was selected, and elemental analysis was performed to confirm its composition. The composition is C 41 H 48It was Cl2SiZr(Mr=731.04): Theoretical values: C, 67.36; H, 6.62; Measured values: C, 67.54; H, 6.56.

[0168] [Synthesized Example 2]

[0169] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(Me 2 NCH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1a)

[0170] 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% volume) were added to the mixture. The mixture was heated at 50°C for 24 hours. All volatile components were removed by vacuuming at room temperature. The remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL each time) of n-hexane. This was vacuum dried for 6 hours to obtain 1.36 g (85.2%) of yellow solid rac-MS-1a.

[0171] Cho Seong-eun C 45 H 57 Cl2NSiZr(Mr=802.16) was: Theoretical values: C, 67.38; H, 7.16; N, 1.75; Measured values: C, 67.42; H, 7.19; N, 1.78.

[0172] [Synthesized Example 3]

[0173] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(Me 2 NCH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H4 C 9 H 4 ) 2 ZrCl 2 Preparation of (meso-MS-1a)

[0174] The execution steps were the same as in Synthesis Example 2, but 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.

[0175] Compounds meso-MS-1 and the aforementioned rac-MS-1 are isomers, and their composition is also C 45 H 57 Cl2NSiZr(Mr=802.16) was: Theoretical values: C, 67.38; H, 7.16; N, 1.75; Measured values: C, 67.44; H, 7.18; N, 1.77.

[0176] [Synthesized Example 4]

[0177] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconium compound Me(PhMeNCH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1b)

[0178] The execution steps were the same as in Synthesis Example 2, but Me2NCH=CH2 was replaced with PhMeNCH=CH2 (0.293g, 2.2mmol) to finally obtain 1.65g (95.9%) of yellow solid rac-MS-1b.

[0179] Cho Seong-eun C 50 H 59Cl2NSiZr(Mr=864.23) was: Theoretical values: C, 69.49; H, 6.88; N, 1.62; Measured values: C, 69.45; H, 6.89; N, 1.65.

[0180] [Synthesized Example 5]

[0181] Aminoalkyl-containing silicon-crosslinked bis-indenosyl zirconocene compound Me(Me 2 NCH 2 CH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1c)

[0182] The execution steps were the same as in Synthesis Example 1, but Me2NCH=CH2 was 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.

[0183] Cho Seong-eun C 46 H 59 Cl2NSiZr(Mr=816.18) was: Theoretical values: C, 67.69; H, 7.29; N, 1.72; Measured values: C, 67.65; H, 7.30; N, 1.70.

[0184] [Synthesized Example 6]

[0185] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(PhMeNCH 2 CH 2 CH 2 )Si(2-Me-7-p- tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1d)

[0186] The execution steps were the same as in Synthesis Example 1, but Me2NCH=CH2 was 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.

[0187] Cho Seong-eun C 51 H 61 Cl2NSiZr(Mr=878.25) was: Theoretical values: C, 69.75; H, 7.00; N, 1.59; Measured values: C, 69.78; H, 7.02; N, 1.60.

[0188] [Synthesized Example 7]

[0189] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(iPr 2 NCH 2 CH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1e)

[0190] The execution steps were the same as in Synthesis Example 1, but Me2NCH=CH2 was replaced with iPr2NCH2CH=CH2 (0.310 g, 2.2 mmol), and finally, 1.54 g (88.8%) of yellow solid rac-MS-1e was obtained.

[0191] Cho Seong-eun C 50 H 67 Cl2NSiZr(Mr=872.29) was: Theoretical values: C, 68.85; H, 7.74; N, 1.61; Measured values: C, 68.83; H, 7.71; N, 1.63.

[0192] [Synthesized Example 8]

[0193] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(iBuMeNCH 2 CH 2 CH 2 CH 2 )Si(2-Me-7-p- tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1f)

[0194] The execution steps were the same as in Synthesis Example 1, but Me2NCH=CH2 was replaced with iBuMeNCH2CH2CH=CH2 (0.310 g, 2.2 mmol), and finally, 1.57 g (90.62%) of yellow solid rac-MS-1f was obtained.

[0195] Cho Seong-eun C 50 H 67 Cl2NSiZr(Mr=872.29) was: Theoretical values: C, 68.85; H, 7.74; N, 1.61; Measured values: C, 68.82; H, 7.72; N, 1.63.

[0196] [Synthesized Example 9]

[0197] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(PhMeNCH 2 CH 2 CH 2 CH 2 )Si(2-Me-7-p- tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1g)

[0198] The execution steps were the same as in Example 1, but Me2NCH=CH2 was replaced with PhMeNCH2CH2CH=CH2 (0.354g, 2.2mmol) to finally obtain 1.64g (92.52%) of yellow solid rac-MS-1g.

[0199] Cho Seong-eun C 52 H 63 Cl2NSiZr(Mr=892.28) was: Theoretical values: C, 70.00; H, 7.12; N, 1.57; Measured values: C, 70.04; H, 7.11; N, 1.59.

[0200] [Synthesized Example 10]

[0201] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(iPrEtNCH 2 CH 2 CH 2 CH 2 )Si(2-Me-7-p- tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1h)

[0202] The execution steps were the same as in Synthesis Example 1, but Me2NCH=CH2 was replaced with iPrEtNCH2CH2CH=CH2 (0.310 g, 2.2 mmol), and finally, 1.57 g (90.61%) of yellow solid rac-MS-1h was obtained.

[0203] Cho Seong-eun C 50 H 71 Cl2NSiZr(Mr=876.32) was: Theoretical values: C, 68.53; H, 8.17; N, 1.60; Measured values: C, 68.51; H, 8.18; N, 1.62.

[0204] [Synthesized Example 11]

[0205] Preparation of Ferrocenylalkenyl-Containing Silicon Crosslinked Bisdenyl Zirconocene Compounds Me(FcCH=CH 2 )Si(2-Me-7-p-tBuC 6H 4 C 9 H 4 ) 2 ZrCl 2 Manufacture of (rac-MS-1i)

[0206] The execution steps were the same as in Synthesis Example 1, except that Me2NCH=CH2 was replaced with FcC≡CH (0.420 g, 2 mmol), and finally, 1.72 g (91.98%) of orange-red solid rac-MS-1i was obtained. In FcC≡CH, Fc=CpFe(C5H4).

[0207] Cho Seong-eun C 53 H 58 Cl2FeSiZr(Mr=941.09) was: Theoretical values: C, 67.64; H, 6.21; Measured values: C, 67.71; H, 6.25.

[0208] [Synthesized Example 12]

[0209] Ferrocenylalkenyl-containing silicone cross-linked bisdenyl zirconocene compound Me(FcCH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-1j)

[0210] The execution steps were the same as in Synthesis Example 1, except that Me2NCH=CH2 was replaced with FcCH=CH2 (0.424 g, 2 mmol), and finally, 1.63 g (87.17%) of orange-red solid rac-MS-1j was obtained. In FcCH=CH2, Fc=CpFe(C5H4).

[0211] Cho Seong-eun C 53 H 60Cl2FeSiZr(Mr=943.10) was: Theoretical values: C, 67.50; H, 6.41; Measured values: C, 67.53; H, 6.43.

[0212] [Preparation of Precursors in Synthesis Examples 13 and 14]

[0213] Hydrogen silicon cross-linked bisindenyl zirconocene compound MeHSi(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 Zr(NMe 2 ) 2 Manufacturing of (rac-MS-2)

[0214] 2-methyl-7-p-tert-butylphenylindene (5.24 g, 20 mmol) was weighed and dissolved in Tol (160 ml) solvent. N-butyllithium (2.4 M, 8.5 ml, 20 mmol) was slowly added dropwise at -78°C. The temperature was slowly raised to room temperature and reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 ml, 10 mmol) was slowly added dropwise to the wine-red solution at 78°C, the temperature was slowly raised to room temperature, and the mixture was stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was filtered, and the LiCl precipitate was removed to obtain a yellow solution. Tetramethylaminozirconium (2.68 g, 10 mmol) was added to the yellow solution while stirring, and the mixture was heated to 70 to 100°C for 12 hours. After cooling to room temperature and removing volatile components, the remaining solid was recrystallized with toluene and hexane to obtain 4.83 g (64.9%) of orange crystalline solid rac-ms-2.

[0215] Cho Seong-eun C 45 H 60 N2SiZr(Mr=748.28) was: Theoretical values: C, 72.23; H, 8.08; N, 3.74; Measured values: C, 72.21; H, 8.05; N, 3.76.

[0216] [Synthesized Example 13]

[0217] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(PhMeNCH 2 CH 2 )Si(2-Me-7-p- tBuC 6 H 4 C 9 H 4 ) 2 Zr(NMe 2 ) 2 Preparation of (rac-MS-2a)

[0218] 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 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.62 g (92.2%) of orange solid rac-MS-2a.

[0219] Cho Seong-eun C 54 H 71 It was N3SiZr(Mr=881.47): Theoretical values: C, 73.58; H, 8.12; N, 4.77; Measured values: C, 73.60; H, 8.14; N, 4.75.

[0220] [Synthesized Example 14]

[0221] Ferrocenylalkenyl-containing silicone cross-linked bisdenyl zirconocene compound Me(FcCH 2 CH 2 )Si(2-Me-7-p-tBuC 6 H 4 C 9 H 4 ) 2 Zr(NMe 2 ) 2 Preparation of (rac-MS-2b)

[0222] The execution steps were the same as in Example 13, except that PhMeNCH=CH2 was replaced with FcCH=CH2 (0.424 g, 2 mmol), and finally, 1.4 g (87.7%) of orange-red solid meso-MS-1a was obtained. In FcCH=CH2, Fc=CpFe(C5H4).

[0223] Cho Seong-eun C 57 H 72 It was N2FeSiZr(Mr=960.35): Theoretical values: C, 71.29; H, 7.56; N, 2.93; Measured values: C, 71.27; H, 7.56; N, 2.91.

[0224] [Preparation of Precursors in Synthesis Examples 15 and 16]

[0225] Hydrogen silicon-based cross-linked bisdenyl zirconocene compound MeHSi(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 Manufacture of (MS-3).

[0226] 2-methyl-7-phenylindene (4.13 g, 20 mmol) was weighed and dissolved in Tol (160 mL) solvent. N-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise to the mixture at -78°C, and the temperature was gradually raised to room temperature and reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly added dropwise to the solution at -78°C, and the temperature was gradually raised to room temperature and stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was left at -78°C, and n-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise to the suspension. After raising to room temperature, the mixture was stirred continuously for 2 hours to obtain a cloudy orange-yellow solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was placed in a vial, 40 mL of toluene was added, and the mixture was placed under nitrogen protection. When zirconium tetrachloride is added to the above-mentioned turbid yellow liquid at room temperature, the color gradually darkens from orange-yellow to brown-black. The reaction was carried out for 1 day. The reaction solution was filtered under nitrogen protection, and the resulting filtrate was desolvated, washed with n-hexane, filtered, and discharged to obtain a yellow solid. The yellow solid was recrystallized in a multi-step process with toluene 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.

[0227] Cho Seong-eun C 33 H 28 Cl2SiZr(Mr=614.79) was: Theoretical values: C, 64.47; H, 4.59; Measured values: C, 64.48; H, 4.61.

[0228] [Synthesized Example 15]

[0229] Aminoalkyl-containing silicon-crosslinked bis-indeneyl zirconocene compound Me(PhMeNCH 2 CH 2 )Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl2 Preparation of (rac-MS-3a)

[0230] 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 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.41 g (87.4%) of orange-red solid rac-MS-3a.

[0231] Cho Seong-eun C 42 H 39 Cl2NSiZr(Mr=747.98) was: Theoretical values: C, 67.44; H, 5.26; N, 1.87; Measured values: C, 67.42; H, 5.27; N, 1.86.

[0232] [Synthesized Example 16]

[0233] Ferrocenylalkenyl-containing silicone cross-linked bisdenyl zirconocene compound Me(FcCH 2 CH 2 )Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 Preparation of (rac-MS-3b)

[0234] The execution steps were the same as in Synthesis Example 13, except that PhMeNCH=CH2 was replaced with FcCH=CH2 (0.424 g, 2 mmol) to finally obtain 1.53 g (86.7%) of orange-red solid rac-MS-3b. In FcCH=CH2, Fc=CpFe(C5H4).

[0235] Cho Seong-eun C 45 H 40 Cl2FeSiZr(Mr=826.86) was: Theoretical values: C, 65.37; H, 4.88; Measured values: C, 65.36; H, 4.89.

[0236] [Preparation of Precursors of Synthesis Examples 16 and 17]

[0237] Hydrogen silicon cross-linked bisfluorenyl zirconocene compound MeHSiFlu 2 ZrCl 2 Manufacturing of (MS-4)

[0238] Fluorene (3.32 g, 20 mmol) was weighed and dissolved in Tol (160 mL) solvent. N-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise at -78°C. Then, the resulting mixture was slowly heated to room temperature and reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly added dropwise to the wine-red solution at -78°C, and after slowly raising the temperature to room temperature, the mixture was stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was kept at -78°C, and n-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise. After heating to room temperature, the mixture was stirred continuously for 2 hours to obtain a cloudy orange-yellow solution. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was placed in a vial, 40 mL of toluene was added, and the vial was placed under nitrogen protection. When zirconium tetrachloride is added to the above-mentioned turbid yellow liquid at room temperature, the color gradually darkens from orange-yellow to brown-black. The reaction was carried out for 1 day. The reaction solution was filtered under nitrogen protection, the resulting filtrate was desolvated, washed with n-hexane, filtered, and discharged to obtain a yellow solid. The yellow solid was recrystallized with toluene at -20°C to obtain 3.89 g (72.8%) of compound MS-4.

[0239] Cho Seong-eun C 27 H 20 Cl2SiZr(Mr=534.66) was: Theoretical values: C, 60.66; H, 3.77; Measured values: C, 60.64; H, 3.74.

[0240] [Synthesized Example 17]

[0241] Aminoalkyl-containing silicon-crosslinked bisperosenyl zirconocene compound Me(PhMeNCH 2 CH 2 )SiFlu 2 ZrCl 2 Manufacture of (MS-4a)

[0242] 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 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.21 g (90.6%) of orange solid MS-4a.

[0243] Cho Seong-eun C 36 H 31 Cl2NSiZr(Mr=667.85) was: Theoretical values: C, 64.74; H, 4.68; N, 2.10; Measured values: C, 64.73; H, 4.71; N, 2.11.

[0244] [Synthesized Example 18]

[0245] Ferrocenyl-containing alkyl silicon cross-linked bisfluorenyl zirconocene compound Me(FcCH 2 CH 2 )SiFlu 2 ZrCl 2 Manufacture of (MS-4b)

[0246] The execution steps were the same as in Synthesis Example 17, except that PhMeNCH=CH2 was replaced with FcCH=CH2 (0.424 g, 2 mmol) to finally obtain 1.32 g (88.4%) of orange solid MS-4b. In FcCH=CH2, Fc=CpFe(C5H4).

[0247] Cho Seong-eun C 39 H 32 Cl2FeSiZr(Mr=746.73) was: Theoretical values: C, 62.73; H, 4.32; Measured values: C, 62.72; H, 4.31.

[0248] [Synthesized Example 19]

[0249] Me[(PhMeN(CH 2 ) 5 )]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0250] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) solvent. PhMeN(CH2)3CH=CH2 (0.388 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, usage 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.49 g (86.2%) of orange-red solid rac-MS-3c.

[0251] Cho Seong-eun C 45 H 45 Cl2NSiZr(Mr=790.97) was: Theoretical values: C, 68.41; H, 5.74; N, 1.77; Measured values: C, 68.44; H, 5.75; N, 1.76.

[0252] [Synthesized Example 20]

[0253] Me[PhMeN(CH 2 ) 8 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0254] 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 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.57 g (86.3%) of orange-red solid rac-MS-3d.

[0255] Cho Seong-eun C 48 H 51 Cl2NSiZr(Mr=832.15) was: Theoretical values: C, 69.28; H, 6.18; N, 1.68; Measured values: C, 69.25; H, 6.16; N, 1.70.

[0256] [Synthesized Example 21]

[0257] Me[PhMeN(CH 2 ) 12 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0258] 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 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.72 g (89.9%) of orange solid rac-MS-3e.

[0259] Cho Seong-eun C 51 H 57 Cl2NSiZr(Mr=874.23) was: Theoretical values: C, 70.07; H, 6.57; N, 1.60; Measured values: C, 70.04; H, 6.55; N, 1.60.

[0260] [Synthesized Example 22]

[0261] Me[PhMeN(CH 2 ) 15 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0262] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) of solvent. PhMeN(CH2) in the mixture 12 CH=CH2 (0.666 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, usage 5%) were added, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum drying was performed for 6 hours to obtain 1.83 g (91.2%) of orange solid rac-MS-3f.

[0263] Cho Seong-eun C 54 H 63 Cl2NSiZr(Mr=916.31) was: Theoretical values: C, 70.78; H, 6.93; N, 1.53; Measured values: C, 70.76; H, 6.95; N, 1.52.

[0264] [Synthesized Example 23]

[0265] Me[p-ClC 6 H 4 MeN(CH 2 ) 5 ]Si(2-Me-7-PhC9 H 4 ) 2 ZrCl 2 manufacturing

[0266] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) of solvent. In the mixture p-ClC 6 H 4 MeN(CH2)3CH=CH2 (0.461 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, usage amount 5%) were added, and the temperature was raised to 50°C and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. After vacuum drying for 6 hours, 1.62 g (90.0%) of the orange-red solid rac-MS-3 g was obtained.

[0267] Cho Seong-eun C 45 H 44 Cl3NSiZr(Mr=824.51) was: Theoretical values: C, 65.55; H, 5.38; N, 1.70; Measured values: C, 65.56; H, 5.36; N, 1.72.

[0268] [Synthesized Example 24]

[0269] Me[p-MeOC 6 H 4 MeN(CH 2 ) 5 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0270] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) of solvent. In the mixture p-MeOC 6 H4 MeN(CH2)3CH=CH2 (0.454 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, usage 5%) were added, and the mixture was heated to 50°C and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. The mixture was vacuum dried for 6 hours to obtain 1.60 g (89.2%) of the orange-red solid rac-MS-3h.

[0271] Cho Seong-eun C 46 H 46 Cl2NOSiZr(Mr=819.09) was: Theoretical values: C, 67.45; H, 5.66; N, 1.71; Measured values: C, 67.47; H, 5.63; N, 1.72.

[0272] [Synthesized Example 25]

[0273] Me[Fc(CH 2 ) 5 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0274] 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 to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.67 g (87.9%) of orange-red solid rac-MS-3i.

[0275] Cho Seong-eun C 48 H 46Cl2FeSiZr(Mr=868.95) was: Theoretical values: C, 66.35; H, 5.34; Measured values: C, 66.36; H, 5.33.

[0276] [Synthesized Example 26]

[0277] Me(Fc(CH 2 ) 8 )Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0278] 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 to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.72 g (86.3%) of orange solid rac-MS-3j.

[0279] Cho Seong-eun C 51 H 52 Cl2FeSiZr(Mr=911.03) was: Theoretical values: C, 65.55; H, 5.38; Measured values: C, 65.56; H, 5.37.

[0280] [Synthesized Example 27]

[0281] Me[Fc(CH 2 ) 12 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0282] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) of solvent. Fc(CH2) 10 CH=CH2 (0.775 g, 2.2 mmol) (Note: Fc=CpFe(C5H4)) and B(C6F5)3 (0.051 g, 0.1 mmol, usage 5%) were added to the mixture and reacted at 50°C for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. It was vacuum dried for 6 hours to obtain 1.98 g (93.6%) of orange-red solid rac-MS-3k.

[0283] Cho Seong-eun C 55 H 60 Cl2FeSiZr(Mr=967.14) was: Theoretical values: C, 68.31; H, 6.25; Measured values: C, 68.34; H, 6.27.

[0284] [Synthesized Example 28]

[0285] Me[Fc(CH 2 ) 15 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0286] Rac-MS-3 (1.34 g, 2 mmol) was weighed and dissolved in Tol (100 mL) of 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 5%) were added to the mixture and reacted at 50°C for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. After vacuum drying for 6 hours, 2.02 g (91.5%) of orange-red solid rac-MS-3L was obtained.

[0287] Cho Seong-eun C 58 H 66 Cl2FeSiZr(Mr=1009.22) was: Theoretical values: C, 69.03; H, 6.59; Measured values: C, 69.04; H, 6.57.

[0288] [Synthesized Example 29]

[0289] R 1 This is a methyl group and R II Metallocene compounds in which alkyl groups are used can be synthesized by referring to the cross-linked SiH group addition method.

[0290] MenBuSi(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0291] 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 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. Vacuum dried for 6 hours to obtain 1.12 g (76.6%) of orange-red solid rac-MS-3m.

[0292] Cho Seong-eun C37 H 36 Cl2SiZr(Mr=670.90) was: Theoretical values: C, 66.24; H, 5.41; Measured values: C, 66.23; H, 5.40.

[0293] [Synthesized Example 30]

[0294] Me[n-CH 3 (CH 2 ) 7 ]Si(2-Me-7-PhC 9 H 4 ) 2 ZrCl 2 manufacturing

[0295] 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 amount 5%) were added to the mixture, heated to 50°C, and reacted for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. After vacuum drying for 6 hours, 1.23 g (77.5%) of orange-red solid rac-MS-3n was obtained.

[0296] Cho Seong-eun C 41 H 44 Cl2SiZr(Mr=727.01) was: Theoretical values: C, 67.74; H, 6.10; Measured values: C, 67.72; H, 6.11.

[0297] [Synthesized Example 31]

[0298] Preparation of MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2.

[0299] 4-phenyl-2-methylindene (2.06 g, 10 mmol) was weighed and dissolved in Tol (80 ml) solvent. N-butyllithium (2.4 M, 4.25 mL, 10 mmol) was slowly added dropwise to the mixture at -78°C, the temperature was gradually raised to room temperature, and the mixture was reacted overnight to obtain a wine-red solution. Methyldichlorosilane (1.04 mL, 10 mmol) was slowly added dropwise to the wine-red solution at -78°C, the temperature was gradually raised to room temperature, and the mixture was stirred for more than 8 hours to obtain a yellow suspension. The yellow suspension was kept at -78°C, lithium tert-butylamine (0.79 g, 10 mmol) was slowly added dropwise to the suspension, and after returning to room temperature, stirring was continued for 2 hours to obtain an orange-yellow cloudy liquid. An orange-yellow cloudy liquid at -78°C was added, and n-butyllithium (2.4 M, 8.5 mL, 20 mmol) was slowly added dropwise. After returning to room temperature, the mixture was stirred continuously for 2 hours to obtain an orange-yellow cloudy liquid. Zirconium tetrachloride (2.33 g, 10 mmol) from a glove box was placed in a vial, 40 mL of toluene was added, and the mixture was placed under nitrogen protection. When zirconium tetrachloride is added to the above yellow cloudy liquid at room temperature, the color immediately darkens from orange-yellow to dark red. The reaction was carried out for 1 day. The reaction solution was filtered under nitrogen protection, the solvent was removed from the obtained filtrate, it was washed with n-hexane, and filtered and discharged to obtain a red solid. The red solid was recrystallized from toluene in multiple steps at -20°C to obtain the compound MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl22.88 g (60.0%).

[0300] Cho Seong-eun C 21 H 25 Cl2NSiZr(Mr=481.65) was: Theoretical values: C, 52.37; H, 5.23; N, 2.91; Measured values: C, 52.40; H, 5.21; N, 2.90.

[0301] [Synthesized Example 32]

[0302] Me[Fc(CH2 ) 5 ]Si(4-Ph-2-MeC 9 H 4 )(NtBu)ZrCl 2 manufacturing

[0303] MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2 (0.96 g, 2 mmol) was weighed and dissolved in Tol (100 mL) of 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 5%) were added to the mixture and reacted at 50°C for 24 hours. All volatile components were removed by vacuum suction at room temperature, and the remaining solid was washed 2 to 4 times with a small amount (approx. 1.5 mL per wash) of n-hexane. It was vacuum dried for 6 hours. Dark red solid Me[Fc(CH 2 ) 5 ]Si(4-Ph-2-MeC 9 H 4 ) (NtBu) ZrCl 2 1.21g (82.1%) was obtained.

[0304] Cho Seong-eun C 36 H 44 Cl2FeNSiZr(Mr=736.81) was: Theoretical values: C, 58.68; H, 6.02; N, 1.90; Measured values: C, 58.66; H, 6.03; N, 1.92.

[0305] B. Preparation of Metallocene Catalysts

[0306] [Preparation Example 1]

[0307] 2 g of silica gel calcined at 600°C was weighed, and 10 mL of 10% MAO (wt%) in toluene was added to the silica gel and heated to 80°C. After uniform stirring, a toluene solution of a metallocene compound represented by Formula 1 was added to the mixture, and the reaction was carried out overnight with the Al / Zr ratio adjusted to 200:1. The solid was collected by filtration, washed with toluene solvent until the washing solvent became colorless, and the solid was dried under vacuum for 24 hours to obtain a solid powder, which was stored in a glove box for future use (this reaction operation method is used unless otherwise specified). Through the supply amount of washing solution and the measurement and calculation of the metal content, catalyst SC-1 with a determined metal content was obtained, and the zirconium content was 0.268% (29.4 μmol / g).

[0308]

[0309] Equation 1

[0310] [Preparation Example 2]

[0311] 2 g of silica gel calcined at 600°C was weighed, 10 mL of 10% MAO (wt%) in toluene and pure toluene solvent were added to the mixture, heated to 80°C, stirred for 24 hours, and then filtered. The solid was collected and washed three times with toluene solvent. The solid was vacuum dried for 24 hours to obtain MAO-silica gel as a solid powder.

[0312] A fixed amount of MAO-silica gel was weighed, and a suspension was formed by adding toluene solvent. A toluene solution of a zirconocene compound was added to the suspension while stirring uniformly, and the reaction was allowed to proceed overnight. The solid was collected by filtration and washed with toluene solvent until the washing solvent became colorless. The solid was vacuum dried for 24 hours to obtain a solid powder, which was stored in a glove box for future use. After measuring and calculating the amount of washing solution supplied and the zirconium content, a catalyst with a specific zirconium content was obtained.

[0313] Catalysts SC-2A (zirconium content 0.846%, 100.2 μmol / g), SC-2B (zirconium content 0.430%, 47.2 μmol / g), and SC-2C (zirconium content 0.282%, 32.2 μmol / g) were prepared by selecting the zirconocene compound of Formula 1 and adjusting the Al / Zr ratio to 50:1, 100:1, and 150:1.

[0314] [Preparation Example 3]

[0315] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound represented by Formula 2 was used, and the Al / Zr ratio was adjusted to 193:1, 227:1, and 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), and SC-3C (zirconium content 0.20%, 16.7 μmol / g), respectively.

[0316]

[0317] Equation 2

[0318] [Preparation Example 4]

[0319] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound represented by Formula 1 was used, and the Al / Zr ratio was adjusted to 193:1, 194:1, and 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), and SC-4C (zirconium content 0.40%, 28.7 μmol / g), respectively.

[0320] [Preparation Example 5]

[0321] The manufacturing steps were the same as those in Preparation Example 2. A metallocene compound as shown in Formula 3 was used, and the Al / Zr ratio was adjusted to 50:1, 100:1, and 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), and SC-5C (zirconium content 0.277%, 30.8 μmol / g), respectively.

[0322]

[0323] Equation 3

[0324] [Preparation Example 6]

[0325] The manufacturing steps were the same as in Manufacturing Example 2. Catalyst SC-6 (zirconium content 0.453%, 51.2 μmol / g) was obtained by using a metallocene compound as shown in Formula 4 and adjusting the Al / Zr ratio to 100:1.

[0326]

[0327] Equation 4

[0328] [Preparation Example 7]

[0329] The manufacturing steps were the same as in Manufacturing Example 2. Catalyst SC-7 (zirconium content 0.441%, 48.7 μmol / g) was obtained by using a metallocene compound as shown in Formula 5 and adjusting the Al / Zr ratio to 100:1.

[0330]

[0331] Equation 5

[0332] [Preparation Example 8]

[0333] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound as shown in Formula 6 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-8 (zirconium content 0.437%, 50.7 μmol / g).

[0334]

[0335] Equation 6

[0336] [Preparation Example 9]

[0337] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound as shown in Formula 7 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-9 (zirconium content 0.463%, 52.4 μmol / g).

[0338]

[0339] Equation 7

[0340] [Preparation Example 10]

[0341] The manufacturing steps were the same as in Manufacturing Example 2. A metallocene compound as shown in Formula 8 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-10 (zirconium content 0.425%, 47.1 μmol / g).

[0342]

[0343] Equation 8

[0344] [Preparation Example 11]

[0345] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound as shown in Formula 9 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-11 (zirconium content 0.439%, 48.3 μmol / g).

[0346]

[0347] Equation 9

[0348] [Preparation Example 12]

[0349] The manufacturing steps were the same as in Manufacturing Example 2. A metallocene compound as shown in Formula 10 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-12 (zirconium content 0.482%, 52.1 μmol / g).

[0350]

[0351] Equation 10

[0352] [Preparation Example 13]

[0353] The manufacturing steps were the same as in Manufacturing Example 2. A metallocene compound as in Formula 11 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-13 (zirconium content 0.501%, 54.3 μmol / g).

[0354]

[0355] Equation 11

[0356] [Preparation Example 14]

[0357] The manufacturing steps were the same as in Manufacturing Example 2. A metallocene compound as shown in Formula 12 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-14 (zirconium content 0.410%, 44.6 μmol / g).

[0358]

[0359] Equation 12

[0360] [Preparation Example 15]

[0361] 2 g of silica gel calcined at 600°C was weighed, 10 mL of 10% (wg%) MAO dissolved in toluene was added to it, and 0.30 g of tetrakis(pentafluorophenyl)borate dioctadecylmethylammonium salt was added to the mixture. Then, 10 mL of toluene was added to the mixture, heated to 80°C, and stirred for 24 hours. The resulting mixture was filtered, the solid was collected, and washed three times with toluene solvent. The solid was vacuum dried for 24 hours to obtain 3.1 g of solid powder-carrier silica gel.

[0362] 2 g of treated carrier silica gel was weighed, and 20 mL of toluene solvent was added to the carrier silica gel to form a suspension. 5 mL of a toluene solution prepared by adding 100 mg of a zirconocene compound represented by Formula 12 was added to the suspension while stirring uniformly, and the mixture was stirred overnight at room temperature. The solid was collected by filtration and washed with toluene solvent until the washing solvent became colorless. The solid was vacuum dried for 24 hours to obtain a solid catalyst powder (SC-15) with a Zr content of 0.390 mass% (42.39 μmol / g), which was stored in a glove box for future use.

[0363] [Preparation Example 16]

[0364] The only difference from Preparation Example 15 was that tris(pentafluorophenyl)borane of the same quality was used to replace tetrakis(pentafluorophenyl)borate dioctadecylmethylammonium salt, no other conditions were changed, and 3.2 g of solid catalyst having a tested zirconium content of 0.45 mass% was obtained.

[0365] [Preparation Example 17]

[0366] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound as shown in Formula 13 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-16 (zirconium content 0.406%, 43.7 μmol / g).

[0367]

[0368] Equation 13

[0369] [Preparation Example 18]

[0370] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound as shown in Formula 14 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-17 (zirconium content 0.415%, 45.9 μmol / g).

[0371]

[0372] Equation 14

[0373] [Preparation Example 19]

[0374] The manufacturing steps were the same as those in Manufacturing Example 2. A metallocene compound as shown in Formula 15 was used, and the Al / Zr ratio was adjusted to 100:1 to obtain catalyst SC-18 (zirconium content 0.371%, 40.2 μmol / g).

[0375]

[0376] Equation 15

[0377] [Preparation Example 20]

[0378] Some of the metallocene compounds from Synthesis Example 2-18 were taken to prepare a catalyst for olefin polymerization. The preparation process was as follows:

[0379] 2 g of silica gel calcined at 600°C was weighed, 10 mL of 10% (wg%) MAO in toluene and 40-100 mL of pure toluene solvent were added, heated to 80°C, and stirred for 24 hours. The resulting mixture was filtered, the solid was collected, and washed three times with toluene solvent. Next, the solid was vacuum dried for 24 hours to obtain a solid powder of MAO-silica gel.

[0380] A certain amount of MAO-silica gel was weighed, and toluene solvent was added to form a suspension. A portion of the toluene solution of the zirconocene compound of the example was added to the suspension while stirring uniformly, and the reaction was allowed to proceed overnight. The solid was filtered and collected, washed with toluene solvent until the washing solvent became colorless, and the solid was vacuum dried for 24 hours to obtain a solid powder, which was stored in a glove box for future use. As a result of measuring and calculating the feed amount and the zirconium content of the washing solution, a catalyst having a specific zirconium content was obtained.

[0381] Among them:

[0382] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound rac-MS-1b was taken to obtain catalyst rac-MS-1b-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0383] The Al / Zr ratio was adjusted to 50:1 and the zirconocene compound rac-MS-1j was taken to obtain catalyst rac-MS-1j-C, with a zirconium content of 0.846% (100.2 μmol / g).

[0384] The Al / Zr ratio was adjusted to 100:1 and the zirconocene compound rac-MS-3a was taken to obtain catalyst rac-MS-3a-C, with a zirconium content of 0.430% (47.2 μmol / g).

[0385] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound rac-MS-3b was taken to obtain catalyst rac-MS-3b-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0386] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound rac-MS-4a was taken to obtain catalyst rac-MS-4a-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0387] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound rac-MS-4b was taken to obtain catalyst rac-MS-4b-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0388] [Preparation Example 21]

[0389] An olefin polymerization catalyst was prepared using the metallocene compound prepared in Synthesis Examples 19-32. The preparation process was as follows:

[0390] 2 g of silica gel calcined at 600°C was weighed, 10 mL of 10% (wg%) MAO in toluene and 40-100 mL of pure toluene solvent were added, heated to 80°C, and stirred for 24 hours. The resulting mixture was filtered, the solid was collected, and washed three times with toluene solvent. Next, the solid was vacuum dried for 24 hours to obtain a solid powder of MAO-silica gel.

[0391] A certain amount of MAO-silica gel was weighed, and toluene solvent was added to form a suspension. A portion of the toluene solution of the zirconocene compound of the example was added to the mixture while stirring uniformly, and the reaction was carried out overnight. The solid was filtered and collected, washed with toluene solvent until the washing solvent became colorless, and the solid was vacuum dried for 24 hours to obtain a solid powder, which was stored in a glove box for future use. As a result of measuring and calculating the feed amount and the zirconium content of the washing solution, a catalyst having a specific zirconium content was obtained.

[0392] Among them:

[0393] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound Me[(PhMeN(CH2)5)]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3c-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0394] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound Me[PhMeN(CH2)8]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3d-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0395] Adjust the Al / Zr ratio to 200:1 and zirconocene compound Me[PhMeN(CH2) 12 ]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3e-C, and the zirconium content was 0.268% (29.4 μmol / g).

[0396] Adjust the Al / Zr ratio to 200:1 and zirconocene compound Me[PhMeN(CH2) 15 ]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain catalyst rac-MS-3f-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0397] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound Me[p-ClC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3g-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0398] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound Me[p-MeOC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3h-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0399] The Al / Zr ratio was adjusted to 200:1, and the zirconocene compound Me[Fc(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain catalyst rac-MS-3i, with a zirconium content of 0.268% (29.4 μmol / g).

[0400] The Al / Zr ratio was adjusted to 200:1, and the zirconocene compound Me(Fc(CH2)8)Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain catalyst rac-MS-3j, with a zirconium content of 0.268% (29.4 μmol / g).

[0401] Adjust the Al / Zr ratio to 200:1 and zirconocene compound Me[Fc(CH2) 12 ]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3k-C, and the zirconium content was 0.268% (29.4 μmol / g).

[0402] Adjust the Al / Zr ratio to 200:1 and zirconocene compound Me[Fc(CH2) 15 ]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain catalyst rac-MS-3l, with a zirconium content of 0.268% (29.4 μmol / g).

[0403] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound MenBuSi(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3m-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0404] The Al / Zr ratio was adjusted to 200:1 and the zirconocene compound Me[n-CH3(CH2)7]Si(2-Me-7-PhC9H4)2ZrCl2 was taken to obtain the catalyst rac-MS-3n-C, with a zirconium content of 0.268% (29.4 μmol / g).

[0405] The Al / Zr ratio was controlled to be 200:1 and the compound MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2 was taken to obtain a catalyst rac-MS-3o-C, wherein the zirconium content was 0.268% (29.4 μmol / g).

[0406] Adjust the Al / Zr ratio to 200:1 and zirconocene compound Me[Fc(CH 2 ) 5 ]Si(4-Ph-2-MeC 9 H 4 )(NtBu ) ZrCl 2 Catalyst rac-MS-3p-C was obtained by taking [the sample], and the zirconium content was 0.268% (29.4 μmol / g).

[0407] C. Catalytic Reaction

[0408] [Example 1]

[0409] Select a 300mL autoclave, vacuum it in an oil bath at 100℃, and replace it with nitrogen three times before use.

[0410] The pressurized catalyst addition device was dried and transferred to a glove box. The measured amount of catalyst was added, along with a small amount of solvent to ensure thorough mixing. The device was removed from the glove box and attached to an autoclave to begin the polymerization experiment.

[0411] The polymerization experimental conditions are as follows: setting specific temperature, pressure, and reaction time. Considering industrial production and applications, the completed polymerization experiments prioritized the selection of co-catalysts, specifically avoiding or minimizing the use of expensive MAO and switching to the use of less expensive alkyl aluminum reagents. (Unless otherwise specified below, this reaction method was used.)

[0412] 200 mg of SC-1 catalyst was used, no solvent was used, the reaction time was 30 minutes, the reaction temperature was 80°C, and 50 g of propylene was compressed into the apparatus.

[0413] Finally, 23.5 g of polymer was obtained, and the calculated activity was 2.35 × 10⁻⁶ 6 g(PP)·mol -1 (Zr)·h -1 It was.

[0414] [Example 2]

[0415] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0416] 105 mg of SC-2A catalyst and 8 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 500:1) were used, and the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was >3.9 MPa.

[0417] Finally, 92 g of polymer was obtained, and the calculated polymerization activity was 4.00 × 10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 131,324, Mw was 325,745, and the PDI value was 2.48, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by 3C NMR spectrum was [mmmm] 99.4%. The melting point was 151.33℃. (Note: PP analysis is optional.)

[0418] [Example 3]

[0419] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0420] 105 mg of SC-2B catalyst and 3.2 mL of triisobutyl aluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was >3.9 MPa.

[0421] Finally, 64g of polymer was obtained, and the calculated polymerization activity was 2.78×10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0422] [Example 4]

[0423] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0424] 106 mg of SC-2C catalyst and 3.2 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 200:1) were used, and the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was >3.9 MPa.

[0425] Finally, 57g of polymer was obtained, and the calculated polymerization activity was 2.45×10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0426] [Example 5]

[0427] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0428] 105 mg of SC-3A catalyst and 8 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 500:1) were used, and the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was >3.9 MPa.

[0429] Finally, 80g of polymer was obtained, and the calculated polymerization activity was 3.48×10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 133,064, Mw was 313,745, and the PDI value was 2.36, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.3%. The melting point test value was 149.43℃.

[0430] [Example 6]

[0431] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0432] 105 mg of SC-3B catalyst and 3.2 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 200:1) were used, and the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was >3.9 MPa.

[0433] Finally, 52g of polymer was obtained, and the calculated polymerization activity was 2.26×10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0434] [Example 7]

[0435] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0436] 106 mg of SC-3C catalyst and 3.2 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 200:1) were used, and the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was >3.9 MPa.

[0437] Finally, 43g of polymer was obtained, and the calculated polymerization activity was 1.85×10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0438] [Example 8]

[0439] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0440] 98 mg of SC-4A catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 528.7 g.

[0441] Finally, 450g of polymer was obtained, and the calculated polymerization activity was 1.098×10⁻⁶ 8g(PP)·mol -1 (Zr)·h -1 It was. Mn was 162,913, Mw was 377,577, and the PDI value was 2.317, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.6%. The melting point test value was 151.4℃.

[0442] [Example 9]

[0443] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0444] 60 mg of SC-4A catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-to-zirconium ratio approximately 896:1) were used, the reaction time was 330 minutes, the reaction temperature was 75℃, and the amount of propylene was 518 g.

[0445] Finally, 860 g of polymer was obtained, and the calculated polymerization activity was 1.772 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 104205, Mw was 226218, and the PDI value was 2.17, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 98.4%. The melting point test value was 152.2 / 161.4℃.

[0446] [Example 10]

[0447] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0448] 60 mg of SC-4A catalyst and 3 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 538 g, and the amount of hydrogen was 0.02 g.

[0449] Finally, 80g of polymer was obtained, and the calculated polymerization activity was 3.186×10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0450] [Example 11]

[0451] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0452] 35 mg of SC-4A catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1707:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0453] Finally, 35 g of polymer was obtained, and the calculated polymerization activity was 2.389 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0454] [Example 12]

[0455] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0456] 65 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1792:1) were used, with a reaction time of 270 minutes, a reaction temperature of 75℃, an amount of propylene of 659 g, and an amount of hydrogen of 0.026 g.

[0457] Finally, 600g of polymer was obtained, and the calculated polymerization activity was 2.206×10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 80551, Mw was 188015, and the PDI value was 2.33, all measured by high-temperature GPC. High temperature 13The isotacticity measured by the 3D NMR spectrum was [mmmm] 99.7%. The melting point test value was 151.83 / 152.2℃.

[0458] [Example 13]

[0459] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0460] 40 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1707:1 by volume) were used, with a reaction time of 180 minutes, a reaction temperature of 75℃, an amount of propylene of 628.6 g, and an amount of hydrogen of 1.365 g.

[0461] Finally, 270g of polymer was obtained, and the calculated polymerization activity was 1.613×10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0462] [Example 14]

[0463] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0464] 30 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 2389:1 by volume) were used, with a reaction time of 360 minutes, a reaction temperature of 75℃, an amount of propylene of 658.8 g, and an amount of hydrogen of 0.052 g.

[0465] Finally, 390 g of polymer was obtained, and the calculated polymerization activity was 3.106 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 Mn was 47736, Mw was 146937, and the PDI value was 3.08, all measured by high-temperature GPC.

[0466] [Example 15]

[0467] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0468] 30 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 2389:1 by volume) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 357.2 g, and the amount of hydrogen was 0.06 g.

[0469] Finally, 205 g of polymer was obtained, and the calculated polymerization activity was 1.633 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was. The melting point test value was 154.03℃.

[0470] [Example 16]

[0471] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0472] 30 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, with a reaction time of 420 minutes, a reaction temperature of 75℃, an amount of propylene of 682 g, and an amount of hydrogen of 0.06 g.

[0473] Finally, 540 g of polymer was obtained, and the calculated polymerization activity was 4.301 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0474] [Example 17]

[0475] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0476] 20 mg of SC-4A catalyst and 3.5 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 627:1) were used, with a reaction time of 180 minutes, a reaction temperature of 75℃, an amount of propylene of 657 g, and an amount of hydrogen of 0.06 g.

[0477] Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 1.195 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0478] [Example 18]

[0479] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0480] 20 mg of SC-4A catalyst and 7 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1254:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 651 g, and the amount of hydrogen was 0.06 g.

[0481] Finally, 45 g of polymer was obtained, and the calculated polymerization activity was 5.376 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0482] [Example 19]

[0483] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0484] 20 mg of SC-4A catalyst, 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1792:1), reaction time 180 min, reaction temperature 75℃, amount of propylene 654 g, and amount of hydrogen 0.06 g.

[0485] Finally, 82 g of polymer was obtained, and the calculated polymerization activity was 9.797 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0486] [Example 20]

[0487] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0488] 20 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-to-zirconium ratio approximately 1792:1) were used, with a reaction time of 180 minutes, a reaction temperature of 75℃, an amount of propylene of 652 g, and an amount of hydrogen of 0.06 g.

[0489] Finally, 92 g of polymer was obtained, and the calculated polymerization activity was 1.099 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0490] [Example 21]

[0491] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0492] 30 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1195:1 by volume) were used, with a reaction time of 420 minutes, a reaction temperature of 75℃, an amount of propylene of 670 g, and an amount of hydrogen of 0.06 g.

[0493] Finally, 530g of polymer was obtained, and the calculated polymerization activity was 4.221×10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0494] [Example 22]

[0495] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0496] 30 mg of SC-4B catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, the reaction time was 480 minutes, the reaction temperature was 75℃, the amount of propylene was 684 g, and the amount of hydrogen was 0.06 g.

[0497] Finally, 610 g of polymer was obtained, and the calculated polymerization activity was 4.859 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0498] [Example 23]

[0499] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0500] 30 mg of SC-4B catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, the amount of propylene was 687.5 g, and the amount of hydrogen was 0.06 g.

[0501] Finally, 533 g of polymer was obtained, and the calculated polymerization activity was 4.245 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was. The melting point test value was 155.46℃.

[0502] [Example 24]

[0503] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0504] 30 mg of SC-4B catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, with a reaction time of 240 minutes, a reaction temperature of 75℃, an amount of propylene of 688.6 g, and an amount of hydrogen of 0.06 g.

[0505] Finally, 405g of polymer was obtained, and the calculated polymerization activity was 3.226×10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0506] [Example 25]

[0507] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0508] 30 mg of SC-4C catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 680 g, and the amount of hydrogen was 0.06 g.

[0509] Finally, 530g of polymer was obtained, and the calculated polymerization activity was 4.221×10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0510] [Example 26]

[0511] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0512] 20 mg of SC-4C catalyst and 10 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 1792:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 681 g, and the amount of hydrogen was 0.06 g.

[0513] Finally, 145 g of polymer was obtained, and the calculated polymerization activity was 1.732 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0514] [Example 27]

[0515] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0516] 98 mg of SC-5A catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum to zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 523 g.

[0517] Finally, 461 g of polymer was obtained, and the calculated polymerization activity was 1.106 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 174,912, Mw was 366,583, and the PDI value was 2.09, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 98.4%. The melting point test value was 153.1℃.

[0518] [Example 28]

[0519] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0520] 60 mg of SC-5B catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 896:1) were used, the reaction time was 330 minutes, the reaction temperature was 75℃, and the amount of propylene was 521 g.

[0521] Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.788 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h-1 It was. Mn was 115,708, Mw was 236,654, and the PDI value was 2.045, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.1%. The melting point test value was 154.9℃.

[0522] [Example 29]

[0523] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0524] 60 mg of SC-5C catalyst and 3 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1195:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 534 g, and the amount of hydrogen was 0.02 g.

[0525] Finally, 91 g of polymer was obtained, and the calculated polymerization activity was 1.641 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0526] [Example 30]

[0527] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0528] 98 mg of SC-6 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 541 g.

[0529] Finally, 424 g of polymer was obtained, and the calculated polymerization activity was 2.112 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 168,742, Mw was 368,213, and the PDI value was 2.18, all measured by high-temperature GPC. High temperature13 The isotacticity measured by the C NMR spectrum was [mmmm] 98.9%. The melting point test value was 155.4℃.

[0530] [Example 31]

[0531] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0532] 100 mg of SC-7 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 539 g.

[0533] Finally, 447 g of polymer was obtained, and the calculated polymerization activity was 2.294 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 19,863, Mw was 398,423, and the PDI value was 2.01, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.2%. The melting point test value was 157.1℃.

[0534] [Example 32]

[0535] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0536] 100 mg of SC-8 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 534 g.

[0537] Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.223 × 10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1It was. Mn was 215,821, Mw was 439,429, and the PDI value was 2.036, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.4%. The melting point test value was 159.1℃.

[0538] [Example 33]

[0539] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0540] 100 mg of SC-9 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 544 g.

[0541] Finally, 472 g of polymer was obtained, and the calculated polymerization activity was 2.252 × 10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 175,941, Mw was 419,745, and the PDI value was 2.386, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.5%. The melting point test value was 161.4℃.

[0542] [Example 34]

[0543] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0544] 100 mg of SC-10 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 521 g.

[0545] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.489 × 10⁻⁶. 7g(PP)·mol -1 (Zr)·h -1 It was. Mn was 155,967, Mw was 430,741, and the PDI value was 2.762, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 97.2%. The melting point test value was 147.9℃.

[0546] [Example 35]

[0547] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0548] 100 mg of SC-11 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 521 g.

[0549] Finally, 471 g of polymer was obtained, and the calculated polymerization activity was 2.437 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 152,134, Mw was 416,572, and the PDI value was 2.738, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 97.5%. The melting point test value was 148.1℃.

[0550] [Example 36]

[0551] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0552] 100 mg of SC-12 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 529 g.

[0553] Finally, 487 g of polymer was obtained, and the calculated polymerization activity was 2.336 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 142,879, Mw was 396,654, and the PDI value was 2.776, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 96.6%. The melting point test value was 144.7℃.

[0554] [Example 37]

[0555] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0556] 100 mg of SC-13 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 542 g.

[0557] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.159 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 162,678, Mw was 396,789, and the PDI value was 2.439, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 97.6%. The melting point test value was 152.9℃.

[0558] [Example 38]

[0559] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0560] 100 mg of SC-14 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 582 g.

[0561] Finally, 459 g of polymer was obtained, and the calculated polymerization activity was 2.573 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 182,668, Mw was 406,769, and the PDI value was 2.226, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 95.6%. The melting point test value was 147.9℃.

[0562] [Example 39]

[0563] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0564] 100 mg of SC-15 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 552 g.

[0565] Finally, 485 g of polymer was obtained. The PDI value measured by high-temperature GPC was 2.028; high temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 96.3%. The melting point test value was 148.5℃.

[0566] [Example 40]

[0567] The evaluation conditions were the same as in Example 39, and the catalyst prepared in Example 16 was used. 300g of polypropylene powder was obtained using 560g of propylene. The PDI measured by GPC was 2.678, and at a high temperature... 13 The isotacticity measured by the C NMR spectrum was [mmmm] 92.6%. The melting point test value was 145.1℃.

[0568] [Example 41]

[0569] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0570] 100 mg of SC-16 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 582 g.

[0571] Finally, 418g of polymer was obtained, and the calculated polymerization activity was 2.434×10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 172,761, Mw was 435,432, and the PDI value was 2.520, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 96.7%. The melting point test value was 148.8℃.

[0572] [Example 42]

[0573] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0574] 100 mg of SC-17 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 582 g.

[0575] Finally, 401 g of polymer was obtained, and the calculated polymerization activity was 2.248 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 123,758, Mw was 467,327, and the PDI value was 3.776, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 92.4%. The tested melting point was 140.2℃.

[0576] [Example 43]

[0577] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0578] 100 mg of SC-18 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 582 g.

[0579] Finally, 491 g of polymer was obtained, and the calculated polymerization activity was 2.752 × 10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 186,469, Mw was 404,219, and the PDI value was 2.168, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 97.2%. The melting point test value was 148.7℃.

[0580] [Example 44]

[0581] For the polymerization reaction, a 300 mL autoclave was used (unless otherwise specified, a 300 mL reactor was used in the following examples), vacuumed in an oil bath at 100°C, and replaced with nitrogen three times before use.

[0582] The pressurized catalyst addition device was dried and transferred to a glove box. The measured amount of catalyst was added, along with a small amount of solvent to ensure thorough mixing. The device was removed from the glove box and attached to an autoclave to begin the polymerization experiment.

[0583] The polymerization experiment conditions are as follows: setting specific temperature, pressure, and reaction time. Considering industrial production and application, the completed polymerization experiment prioritized the selection of co-catalysts, namely avoiding or minimizing the use of expensive MAO and switching to the use of cheaper alkyl aluminum reagents.

[0584] 50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum / zirconium ratio approximately 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.

[0585] Finally, 10g of polymer was obtained, and the calculated polymerization activity was 6.8×10 6 g(PE)·mol -1 (Zr)·h -1 It was.

[0586] [Example 45]

[0587] The polymerization conditions were basically the same as in Example 44, except that 50 mg of rac-MS-1b-C catalyst was reacted with 2 mL of triisobutyl aluminum (concentration 150 μmol / mL, aluminum / zirconium ratio about 200), the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 2 MPa.

[0588] Finally, 16 g of polymer was obtained, and the calculated polymerization activity was 1.08 × 10⁻⁶ 7 g(PE)·mol -1 (Zr)·h -1 It was.

[0589] [Example 46]

[0590] The polymerization conditions were basically the same as in Example 44, except that 150 mg of rac-MS-1b-C catalyst and 0.2 mL of MAO (10 mass% of Tol, aluminum / zirconium ratio about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 1 MPa.

[0591] Finally, 35g of polymer was obtained, and the calculated polymerization activity was 6.99×10⁻⁶. 6 g(PE)·mol -1 (Zr)·h -1 It was.

[0592] [Example 47]

[0593] The polymerization conditions were basically the same as in Example 44, except that 113 mg of rac-MS-1j-C catalyst and 15 mL of triisobutyl aluminum solution (concentration 150 μmol / mL, aluminum / zirconium ratio about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 1 MPa.

[0594] Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 0.88 × 10⁻⁶ 6 g(PE)·mol -1 (Zr)·h -1 It was.

[0595] [Example 48]

[0596] The polymerization conditions were basically the same as in Example 44, except that 150 mg of rac-MS-3a-C catalyst and 6.3 mL of triisobutyl aluminum (concentration 150 μmol / mL, aluminum / zirconium ratio about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50℃, and the ethylene pressure was 1 MPa.

[0597] Finally, 21g of polymer was obtained, and the calculated polymerization activity was 4.45×10⁻⁶ 6 g(PE)·mol -1 (Zr)·h -1 It was.

[0598] [Example 49]

[0599] The polymerization conditions were basically the same as in Example 44, except that 150 mg of rac-MS-3b-C catalyst and 1.75 mL of triisobutyl aluminum (concentration 150 μmol / mL, aluminum-zirconium ratio about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50℃, and the ethylene pressure was 1 MPa.

[0600] Finally, 36g of polymer was obtained, and the calculated polymerization activity was 2.74×10⁻⁶ 7 g(PE)·mol -1 (Zr)·h -1 It was.

[0601] [Example 50]

[0602] The polymerization conditions were basically the same as in Example 44, except that 150 mg of rac-MS-4a-C catalyst and 6.3 mL of triisobutyl aluminum (concentration 150 μmol / mL, aluminum / zirconium ratio about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50℃, and the ethylene pressure was 1 MPa.

[0603] Finally, 54g of polymer was obtained, and the calculated polymerization activity was 1.22×10⁻⁶ 7 g(PE)·mol -1 (Zr)·h -1 It was.

[0604] [Example 51]

[0605] The polymerization conditions were basically the same as in Example 44, except that 150 mg of rac-MS-4b-C catalyst and 3.75 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio about 200:1) were used, the reaction time was 60 minutes, the reaction temperature was 50℃, and the ethylene pressure was 2 MPa.

[0606] Finally, 62 g of polymer was obtained, and the calculated polymerization activity was 1.41 × 10⁻⁶. 7 g(PE)·mol -1 (Zr)·h -1 It was.

[0607] [Example 52]

[0608] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0609] 112 mg of rac-MS-1b-C catalyst and 8 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 500:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was > 3.9 MPa.

[0610] Finally, 91g of polymer was obtained, and the calculated polymerization activity was 9.20×10⁻⁶ 6 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 133,945, Mw was 342,375, and the PDI value was 2.57, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.3%. The melting point test value was 157.63℃.

[0611] [Example 53]

[0612] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0613] 101 mg of rac-MS-1j-C catalyst and 3.2 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, and the propylene pressure was > 3.9 MPa.

[0614] Finally, 132 g of polymer was obtained, and the calculated polymerization activity was 4.33 × 10⁻⁶ 6 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 127361, Mw was 36.431, and the PDI value was 2.83, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 98.6%. The melting point test value was 152.3℃.

[0615] [Example 54]

[0616] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0617] 104 mg of rac-MS-1b-C catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, and the amount of propylene was 528.7 g.

[0618] Finally, 412 g of polymer was obtained, and the calculated polymerization activity was 33.37 × 10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 173,453, Mw was 394,257, and the PDI value was 2.273, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 99.1%. The melting point test value was 154.4℃.

[0619] [Example 55]

[0620] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0621] 104 mg of rac-MS-1b-C catalyst and 15 mL of triethylaluminum (concentration 150 μmol / mL, aluminum-zirconium ratio approximately 549:1) were used, the reaction time was 240 minutes, the reaction temperature was 75℃, the amount of propylene was 538 g, and the amount of hydrogen was 0.02 g.

[0622] Finally, 478 g of polymer was obtained, and the calculated polymerization activity was 1.54 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 135,427, Mw was 397,892, and the PDI value was 2.938, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 98.4%. The melting point test value was 153.2℃.

[0623] [Example 56]

[0624] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0625] 35 mg of rac-MS-1j-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1707:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0626] Finally, 135g of polymer was obtained, and the calculated polymerization activity was 4.37×10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was. Mn was 82451, Mw was 213509, and the PDI value was 2.59, all measured by high-temperature GPC. High temperature 13 The isotacticity measured by the C NMR spectrum was [mmmm] 96.7%. The melting point test value was 147.83 / 150.2℃.

[0627] [Example 57]

[0628] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0629] 35 mg of rac-MS-3c-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0630] Finally, 469g of polymer was obtained, and the calculated polymerization activity was 1.52×10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0631] [Example 58]

[0632] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0633] 35 mg of rac-MS-3d-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0634] Finally, 455g of polymer was obtained, and the calculated polymerization activity was 1.47×10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0635] [Example 59]

[0636] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0637] 35 mg of rac-MS-3e-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0638] Finally, 492 g of polymer was obtained, and the calculated polymerization activity was 1.59 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0639] [Example 60]

[0640] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0641] 35 mg of rac-MS-3f-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0642] Finally, 421 g of polymer was obtained, and the calculated polymerization activity was 1.36 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0643] [Example 61]

[0644] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0645] 35 mg of rac-MS-3g-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1), reaction time 180 min, reaction temperature 75℃, amount of propylene 512 g, and amount of hydrogen 0.02 g.

[0646] Finally, 387 g of polymer was obtained, and the calculated polymerization activity was 1.25 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0647] [Example 62]

[0648] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0649] 35 mg of rac-MS-3h-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum to zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0650] Finally, 418g of polymer was obtained, and the calculated polymerization activity was 1.35×10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0651] [Example 63]

[0652] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0653] 35 mg of rac-MS-3i-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0654] Finally, 441 g of polymer was obtained, and the calculated polymerization activity was 1.43 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0655] [Example 64]

[0656] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0657] 35 mg of rac-MS-3j-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0658] Finally, 427 g of polymer was obtained, and the calculated polymerization activity was 1.38 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0659] [Example 65]

[0660] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0661] 35 mg of rac-MS-3k-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0662] Finally, 434g of polymer was obtained, and the calculated polymerization activity was 1.41×10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0663] [Example 66]

[0664] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0665] 35 mg of rac-MS-3l-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0666] Finally, 395 g of polymer was obtained, and the calculated polymerization activity was 1.27 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0667] [Example 67]

[0668] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0669] 35 mg of rac-MS-3p-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0670] Finally, 352 g of polymer was obtained, and the calculated polymerization activity was 1.14 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0671] [Comparative Example 1]

[0672] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0673] 35 mg of rac-MS-3m-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1), reaction time 180 min, reaction temperature 75℃, amount of propylene 512 g, and amount of hydrogen 0.02 g.

[0674] Finally, 425 g of polymer was obtained, and the calculated polymerization activity was 1.38 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0675] [Comparative Example 2]

[0676] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0677] 35 mg of rac-MS-3n-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0678] Finally, 420g of polymer was obtained, and the calculated polymerization activity was 1.36×10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 It was.

[0679] [Comparative Example 3]

[0680] Selected a 2000mL autoclave, vacuumed it in an oil bath at 100℃, and replaced it with nitrogen three times before use.

[0681] 35 mg of rac-MS-3o-C catalyst and 2.5 mL of triethylaluminum (concentration 100 μmol / mL, aluminum-zirconium ratio approximately 1200:1) were used, the reaction time was 180 minutes, the reaction temperature was 75℃, the amount of propylene was 512 g, and the amount of hydrogen was 0.02 g.

[0682] Finally, 268 g of polymer was obtained, and the calculated polymerization activity was 8.68 × 10⁻⁶ 7 g(PP)·mol -1 (Zr)·h -1 It was.

[0683] The above experimental data is organized in the following table to facilitate comparison and analysis.

[0684] [Table 1]

[0685]

[0686] [Table 2]

[0687]

[0688] [Table 3]

[0689]

[0690] Note: In Table 1-3, the catalytic active unit of Example 1-43 is 10 6 g(PP)·mol-1(Zr)·h -1 is. "--" means that there is no corresponding data.

[0691] According to the data in Table 1-3:

[0692] 1) When the substituents on the crosslinking atoms of the metallocene compound include amine-substituted C2-C4 groups or metallocene-substituted C1-C3 groups, the prepared catalyst has higher catalytic activity for the polymerization of propylene and yields a polymerization product having appropriate molecular weight, PDI value, isotacticity, and melting point.

[0693] 2) By adjusting the type of substituent on the crosslinking atoms of metallocene compounds, polymerization products with different molecular weights and melting points can be obtained.

[0694] 3) As exemplified in Examples 1-4 and 8-11, the polymerization activity of the catalyst can be further optimized by adjusting test conditions such as the Al / Zr ratio of the catalyst and / or the Al / Zr ratio of the polymerization system.

[0695] [Table 4]

[0696]

[0697] Note: In Examples 44-51, the unit of catalytic activity is 10 6 g(PE)·mol -1 (Zr)·h -1 am.

[0698] According to the data in Table 4:

[0699] 1) When the substituents on the crosslinking atoms of the metallocene compound include amine-substituted C2 groups or metallocene-substituted C2 groups, the prepared catalyst has higher catalytic activity for ethylene polymerization.

[0700] 2) As exemplified in Examples 44-45, the polymerization activity of the catalyst can be further optimized by adjusting test conditions such as the Al / Zr ratio of the catalyst and / or the Al / Zr ratio of the polymerization system.

[0701] [Table 5]

[0702]

[0703] Note: In Table 5, the catalytic active units of Examples 52-58 are 10 6g(PP)·mol -1 (Zr)·h -1 am.

[0704] According to the data in Table 5:

[0705] 1) When the substituent on the crosslinking atom in the metallocene compound includes an amine-substituted C2 group or a metallocene-substituted C2 group, the prepared catalyst has higher catalytic activity for propylene polymerization.

[0706] 2) As exemplified in Examples 52, 54 and 56, the polymerization activity of the catalyst can be further optimized by adjusting test conditions such as the Al / Zr ratio of the catalyst and / or the Al / Zr ratio of the polymerization system.

[0707] [Table 6]

[0708]

[0709] Note: In Table 6, the catalytic active units of Examples 57-67 are 10 6 g(PP)·mol -1 (Zr)·h -1 is. "--" means that there is no corresponding data.

[0710] According to the data in Table 6:

[0711] C5-C metallocene compounds in which substituents on the crosslinking atoms are substituted with amine groups 15 C5-C substituted with a group or metallocene group 15 In this case, the manufactured catalyst has higher catalytic activity for propylene polymerization.

[0712] According to the data in Table 1-6:

[0713] Compared to substituents on the cross-linking atoms of metallocene compounds that do not contain amine-substituents or metallocene-substituents, when the substituents on the cross-linking atoms of metallocene compounds are amine-substituents or metallocene-substituents, the prepared catalyst has higher catalytic activity for propylene polymerization.

Claims

Claim 1 Metallocene compounds having a structure represented by the following formula (I): In Equation (I), R I and R II One of them is selected from amino-substituted C1-C6 hydrocarbyl, amino-substituted C1-C6 halohydrocarbyl groups; or R I and R II One of them is selected from metallocene-substituted C1-C6 hydrocarbil and metallocene-substituted C1-C6 halohydrocarbil; R I and R II The other one is selected from C1-C6 hydrocarbyl; Z is silicon; and Cp III As shown in Formula (II), is a cyclopentadienyl containing a substituent, an indenyl containing a substituent, or a fluorenyl containing a substituent, and R i , R ii , and R iii is a substituent within the corresponding ring; Formula (II)R i , R ii and R iii Linear or branched saturated or unsaturated C1-C atoms that are identical or different and each independently contain or do not contain hydrogen or heteroatoms. 20 Hydrocarbyl; and R i , R ii and R iii is not simultaneously hydrogen; E is NR iv or PR iv Igo;R iv is a linear or branched saturated or unsaturated C1-C that contains or does not contain hydrogen and heteroatoms. 20 Selected from hydrocarbyl; M is selected from Ti, Zr, and Hf; L IV and L V are linear or branched saturated or unsaturated C1-C atoms that are identical or different and each independently contain or do not contain hydrogen, chlorine, dimethylamino, or heteroatoms. 20 It is hydrocarbyl; and n is 2. Claim 2 A metallocene compound according to claim 1, wherein the amino is represented by the following formula (III): In Equation (III), R a and R b are identical or different, and each independently hydrogen, C1-C6 alkyl, C6-C 18 Aryl, C7-C 20 Arylalkyl, and C7-C 20 Alkylaryl, or C1-C6 alkyl, C6-C 12 Aryl, and C7-C 10 Selected from arylalkyl, or C1-C4 alkyl, phenyl, and C7-C9 arylalkyl; and the metal of the metallocene group is Fe, and the metallocene group is ferrocenyl. Claim 3 In paragraph 1, in formula (I), L IV and L V A metallocene compound that is identical and is selected from hydrogen, chlorine, methyl, phenyl, benzyl, and dimethylamino. Claim 4 A method for preparing a metallocene compound of claim 1, wherein the method comprises the following: S1. H2(Cp III React ) with an alkali metal-organic compound to obtain the corresponding [H(Cp III )] - Step of forming an alkali metal salt; S2. [H(Cp III )] - Alkali metal salts R I R II React with ZX2 to R I R II Z[H(Cp III Step of forming )]2; S3. R I R II Z[H(Cp III React )]2 with an alkali metal-organic compound to obtain the corresponding R I R II Z(Cp III )2 2- Step of forming an alkali metal salt; and S4. R I R II Z(Cp III )2 2- 2 ml of alkali metal salt IV L V By reacting with to cause a salt removal reaction, R I R II Z(Cp III )2ML IV L V A step of obtaining; wherein X is selected from Cl, Br, and I; where, in S4, R I R II Z(Cp III )2 2- Alkali metal salts are directly x2 ml without separation. IV L V A manufacturing method that causes a salt removal reaction by reacting with Claim 5 Precursor R I HZ(Cp III ) n (E) 2-n ML IV L V and R II A method for preparing a metallocene compound according to claim 1, comprising the step of preparing a metallocene compound by performing a Z hydrogenation reaction between precursors, wherein R II A method for manufacturing, wherein the precursor is a molecule containing multiple bonds, wherein the molecule containing multiple bonds is selected from organic multiple bond molecules, CO and CO2, and the multiple bonds are selected from group 13 to 16 elements of the same or different atoms, or are one or more bonds selected from C=C, C≡C, C=N, C≡N, C=O, C≡P, N=N, C=S, C=C=C, C=C=N, C=C=O, and N=C=N. Claim 6 In claim 5, the Z hydrogenation reaction is carried out in the presence of a catalyst, said catalyst is selected from one or more of transition metal catalysts and Lewis acid catalysts, or selected from one or more of a platinum catalyst of a transition metal catalyst and a B(C6F5)3 catalyst of a Lewis acid; and / or the amount of catalyst used in the Z hydrogenation reaction is 0.00001-50% or 0.01-20% of the total mass of the reactants; and / or the temperature of the Z hydrogenation reaction is -30 to 140°C or 0 to 90°C; and / or the reaction time of the Z hydrogenation reaction is greater than 0.1h or 2-50h; and / or the obtained precursor is separated or purified by recrystallization, said solvent for recrystallization is an aprotic solvent; Or, the solvent is one or more selected from linear or branched alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, ether compounds and cyclic ether compounds; or one or more selected from toluene, xylene, hexane, heptane, cyclohexane and methylcyclohexane, a method for preparation. Claim 7 In paragraph 5, precursor R I HZ(Cp III ) n (E) 2-n ML IV L V is prepared by a one-pot method of chemical reaction; precursor R I HZ(Cp III ) n (E) 2-n ML IV L V The method of manufacturing comprises the following: Step 1) H2(Cp III React ) with an alkali metal-organic compound to obtain the corresponding [H(Cp III )] - Step 2) forming an alkali metal salt; Step 2) [H(Cp III )] - Alkali metal salts R I React with HZX2 to R I HZ[H(Cp III Step of forming )]2; Step 3) R I HZ[H(Cp III )]2 without separation L viii L viv ML IV L V stable small molecule L by direct reaction with viii or L viv By removing precursor R I HZ(Cp III )2ML IV L V Step of obtaining; and / or R I HZ[H(Cp III A step of forming an alkali metal salt by directly reacting )]2 with an alkali metal-organic compound without separation; x2 mL of the obtained alkali metal salt IV L V React with to cause a salt removal reaction, thereby producing precursor R I HZ(Cp III )2ML IV L V A step of obtaining; wherein X is selected from Cl, Br, and I. Claim 8 A method of manufacturing according to claim 4 or 5, wherein, in each step, the reaction temperature of the reaction is in the range of -100°C to 140°C or in the range of -85°C to 110°C; and / or the reaction time is greater than 0.016h or 2 to 100 hours; wherein, in each step, the reaction materials are mixed at a temperature of -100°C to -20°C or -85°C to -10°C, and the mixed reaction materials are reacted at 10°C to 50°C or 20°C to 35°C for 1 hour to 100h or 5h to 50h. Claim 9 A method of preparation according to claim 4 or 5, wherein at each step, the reaction is carried out in an aprotic solvent selected from linear or branched alkanes, cycloalkanes, aromatic compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, or in one or more of toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether, and dioxane; and / or the alkali metal-organic compound is selected from hydrogenated metals, alkyl metals, alkenyl metals, aromatic metals and amine metals, or alkyl metals, or C1-C6 alkyl metals; and / or the alkali metal is selected from Li, Na, and K, or is Li. Claim 10 A catalyst for an α-olefin polymerization reaction comprising the metallocene compound of claim 1, a co-catalyst, and a support. Claim 11 A catalyst according to claim 10, wherein the co-catalyst is selected from one or more of a Lewis acid and an ionic compound containing a Lewis acid or a non-coordinate anion and a Brønsted acid cation; wherein the Lewis acid comprises one or more of alkyl aluminum, alkyl aluminoxane, and organic borides; and / or the ionic compound containing a Lewis acid or a non-coordinate anion and a Brønsted acid cation is selected from a compound containing one to four perfluoroaryl-substituted borate anions. Claim 12 In claim 11, the alkyl aluminum comprises trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-n-butyl aluminum, tri-isoamyl aluminum, tri-n-amyl aluminum, tri-isohexyl aluminum, tri-n-hexyl aluminum, tri-isoheptyl aluminum, tri-n-heptyl aluminum, tri-isooctyl aluminum, tri-n-octyl aluminum, tri-isononyl aluminum, tri-n-nonyl aluminum, tri-isodecyl aluminum and tri-n-decyl aluminum; and / or the alkyl aluminoxane comprises methyl aluminoxane, ethyl aluminoxane and butyl-modified aluminoxane; and / or the organic boride comprises trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and tris(2,4,6-trifluorophenyl)borane; and / or the perfluoroaryl group is selected from perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, and perfluoroalkylphenyl, and the cation is selected from n,n-dimethylphenylammonium ion, triphenylcarbonium ion, trialkylammonium ion, and triarylammonium ion, wherein the catalyst is selected from n,n-dimethylphenylammonium ion, triphenylcarbonium ion, trialkylammonium ion, and triarylammonium ion. Claim 13 In claim 10, the catalyst wherein the content of the metallocene compound calculated based on the M element is 0.001 mass% to 10 mass%, or 0.01 mass% to 1 mass%; and / or the molar ratio of the Al element of the co-catalyst to the M element of the metallocene compound is (1 to 500):1, or (50 to 300):

1. Claim 14 A method for manufacturing a catalyst according to claim 10, comprising the step of forming a catalyst by combining a metallocene compound, a co-catalyst, and a support under the action of a solvent, wherein the combination conditions include a combination temperature of -40°C to 200°C or 40°C to 120°C; and a combination time of greater than 0.016h or 2h to 100h. Claim 15 A method for preparing a catalyst according to claim 14, wherein the solvent is selected from one or more of linear hydrocarbons, branched hydrocarbons, cyclic saturated hydrocarbons and aromatic hydrocarbons, or is selected from one or more of toluene, xylene, n-butane, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane and neoheptane. Claim 16 A metallocene compound used in the field of α-olefin polymerization according to claim 1. Claim 17 In claim 16, the polymerization reaction of an α-olefin is carried out in the presence of a metallocene compound to obtain a poly-α-olefin, and said polymerization reaction is carried out without a solvent, the metallocene compound. Claim 18 A metallocene compound according to claim 16, wherein the conditions of the polymerization reaction include a reaction temperature of -50°C to 200°C or 30°C to 100°C; and a reaction time of 0.01h to 60h or 0.1h to 10h. Claim 19 A metallocene compound according to claim 16, wherein the amount of metallocene catalyst or metallocene catalyst system used per gram of α-olefin is 0.001 mg to 1000 mg, or 0.01 mg to 200 mg, or 0.1 mg to 20 mg. Claim 20 In paragraph 16, the α-olefin is C2-C 20 α-olefin, or C2-C 14 A metallocene compound comprising α-olefin, or ethylene, propylene, 1-butene, 1-pentene, -hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tritecene, 1-tetradecene, 1-pentadecene, 1-heptadiene, 1-octadecene and 1-eicocene, or 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tritecene or 1-tetradecene.

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