Metallocene compounds, methods for producing the same, and applications

Abstract

The present invention provides a metallocene compound that has high catalytic activity and enables the synthesis of metallocene polypropylene with high isotacticity. [Solution] The metallocene compound of the present invention has the structure shown in formula (I). The groups linked to the crosslinking atoms of the metallocene compound are groups substituted with amine groups and / or groups substituted with metallocene groups and / or substituted metallocene groups. Due to this special structure, the metallocene catalyst containing the metallocene compound has high catalytic activity and can synthesize metallocene polypropylene with high isotacticity. JPEG2026123034000028.jpg21169

Description

Detailed description of the invention

[0001] This application requests priority from the following patent application filed on October 30, 2019.

[0002] 1. A Chinese patent application with the title of "Asymmetric Crosslinked Diindenyl Group Metallocene Transition Metal Catalyst, Method for Production and Application" and application number CN201911047955.1.

[0003] 2. A Chinese patent application whose title is "Silicon-linked metallocene compound, method for producing the same, and application," and whose application number is CN201911046672.5.

[0004] All of those contents are incorporated herein by reference.

[0005] [Technical Field] The present invention relates to metallocene compounds, methods for producing the same, and applications, and more particularly to metallocene catalysts containing the metallocene compound, methods for producing the catalyst, and applications, and more specifically, to the technical field of metallocene catalysts.

[0006] [Background technology] Metallocene polypropylene (mPP) exhibits excellent applicability in the areas of fibers, injection molding, and film products, and market demand has been increasing year by year in recent years. These resin products have high demands for the stereoregularity of polypropylene, and the structure of polypropylene is adjusted and controlled by the structure of a catalyst.

[0007] Metallocene polypropylenes with high isotacticity are an important resin variety, and they are synthesized by controlling the chain extension of propylene using a catalytic stereoenograph site. Catalysts capable of carrying out reactions that control chain extension using a stereoenograph site must have C2 axis symmetry or lower C1 axis symmetry (Chem. Rev. 2000, 100, 1223), and racemic cross-linked bisindene ring compounds and their derivative systems of Group 4 metals such as titanium, zirconium, and hafnium compounds possess these characteristics. In the 1980s, Brintzinger synthesized racemic ethyldiindene ligands and subsequent ethyldi(tetrahydroindene) ligands (J. Organomet. Chem. 1982, 232, 233; 1985, 288, 63). While these titanium and zirconium compounds, with the help of methylaluminoxane (MAO) additives, catalyze propylene to produce polypropylene with high isotacticity, mesostructure catalysts cannot produce polypropylene with high isotacticity. The reaction activity, molecular weight, and isotacticity of these racemic catalysts are greatly affected by temperature. Within the range of -20 to 60°C, the difference between the highest (84.43 kgPP / gZr·h) and lowest (0.88 kgPP / gZr·h) activities is nearly two orders of magnitude, and the average molecular weight of the highest (300,000 daltons) and lowest (12,000 daltons) differs by 25 times. However, the change in the molecular weight distribution of the polymer is not large, varying between 1.9 and 2.6, and the isotacticity is within the range of [mmmm]86.0 to 91.0 (Angew. Chem. Int. Ed. Engl. 1985, 24, 507). In 1989, Herrmann et al. synthesized a racemic silicon-bridged indene zirconium compound. Subsequently, Spalleck and Herrmann et al. performed substituent modifications on the indene ring. The catalyzed polypropylene produced under high temperature and MAO action approaches and reaches industrial application levels in terms of reaction activity, molecular weight, molecular weight distribution, and isotacticity (up to 98% at mp152°C) (Angew. Chem. Int. Ed. Engl. 1989, 28, 1511; 1992, 31, 1348).As a result, a series of cross-linked bisindenyl and its derivative system Group 4 metallocene catalysts have been successively developed and used for the isotactic polymerization catalysis of propylene (Chem.Rev.2000,100,1253).

[0008] Reaction conditions, for example, factors such as temperature, pressure, time, and the catalyst concentration, solvent, auxiliary agent, impurity remover, hydrogen molecule regulator, etc. have a great influence on the catalytic reaction to produce highly isotactic polypropylene, but the regulatory control effect of the stereoscopic mirror image sites of the racemic structure plays an essential and decisive role. These structural features are mainly embodied in five aspects: the indenyl ring, indenyl ring substituents, cross-linking groups, central metal, and groups that can cause chain extension by bonding with the central metal. It is clear that researchers in this field can obtain corresponding patents even with any innovation in the characteristics of these five aspects.

[0009] This patent application mainly relates to the important role of the cross-linking group. According to the definition of the cross-linking group S in the conventional US Patents US5017714 and US5120867 ′ it means a silylene group, silyl group, oxy silylene group, or oxy silyl group of 1 to 4 atoms containing silicon group cross-linking. Subsequently, Patent US5145819 gave a broad definition and patent protection to the cross-linking -(CR 8 R 9 ) m -R 7 -(CR 8 R 9 ) n - structural group, where R 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 )-, -O-M 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 It is specified that, here, R 11 , R 12 , R 13 These groups may be the same or different, and these groups may be H, halogen atoms, C1-C 10 Alkyl alkyl groups, C1-C 10 Fluoroalkyl groups, C6-C 10 Aryl group, C6~C 10 Fluoroaryl group, C1-C 10 Alkoxy group, C2~C 10 Alkenyl group, C7~C 40 It is an aryl group-substituted alkyl group, or R 11 and R 12 and R 11 and R 13 It is bonded together as a ring by atoms, M 2 These are Si, Ge, and Sn, and R 8 and R 9 They may be the same or different, and the specific definition of the base is R 11 This is the same as m and n may be the same or different, and they are 0, 1 or 2, or m+n is 0, 1 or 2. In these definitions, R 7 is -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 takes precedence over. US5239022 further defines alkyl groups as linear or branched alkyl groups, halogen atoms as fluorine, chlorine, bromine, iodine, and R 11, R 12 , R 13 Specify the group R specifically and preferentially. For details, refer to the original document. In patents US5243011, US5276208, US5350817, US5374752, US5483002, US5672668, US5714427, US5741868, US6087291, US6114479, US6124230, US6228795B1, US2003 / 0088022A1, the definition of the crosslinking group is similar to it. In US5770753, the crosslinking group is directly defined as R 13 and the specific types are -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 )-, -O-M 2 (R 14 )(R 15 )-O-, -C(R 14 )(R 15 )-, -O-M 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 are included, where R 14 and R 15 may be the same or different, and these groups are H, halogen atom, C1 - C10 Alkyl alkyl groups, C1-C 10 Fluoroalkyl groups, C1-C 10 Alkoxy group, C6~C 10 Aryl group, C6~C 10 Fluoroaryl group, C6~C 10 Phenolic group, C2~C 10 Alkenyl group, C7~C 40 Aryl group-substituted alkyl groups, C7~C 40 Alkyl-substituted aryl group 、 C8~C 40 Aryl group-substituted alkenyl group, or R 14 and R 15 It is bonded by atoms as one or more rings, M 2 These are Si, Ge, and Sn. Subsequent patents US5786432, US5380821, US5840644, US5840948, US5852142, US5929264, US5932669, US6051522, US60517272, US6057408, US6242544B1, US6255506B1, US6376407B1, US Similar or substantially identical crosslinking group structures are mentioned in 63764408B1, US63764409B1, US63764410B1, US63764411B1, US63764412B1, US2001 / 0021755A1, US2006 / 0116490A1, and US2006 / 0252637A1. In US63764413B1, the crosslinking group is biphenylyl-M 2 (C6R 17 R 18 R 19 R 20 -C6R 21 R 22 R 23 R 24 )- is defined as, R 17 ~R 24 As a general definition, R 1 and R 2 The specified or two or more adjacent radicals R 17 ~R 24 And R 20 and R 21 It contains and is linked by atoms to form one or more rings, R 17~R 24 H is preferred. 1 and R 2 They may be the same or different, and these are one of H, C1~C 10 Alkyl alkyl groups, C1-C 10 Alkoxy group, C6~C 10 Aryl group, C6~C 10 Phenolic group, C2~C 10 Alkenyl group 、 C7~C 40 Aryl group-substituted alkyl groups, C7~C 40 Alkyl-substituted aryl group, C8~C 40 These include aryl-substituted alkenyl groups, OH groups, halogen atoms, or conjugated dienes (optionally substituted with one or more hydrocarbon groups), trihydrocarbon silicon groups or trihydrocarbon groups, and trihydrocarbon silicon-substituted hydrocarbon groups (where the number of non-hydrogen atoms reaches 30). Such patents include US5616747, US6376627B1, US6380120B1, US6380121B1, US6380122B1, US6380123B1, US6380124B1, US6380130B1, US6380134B1, etc. Patents US5391790 and US5616747 are directly -R 6 - indicates a crosslinking group, -[M 2 (R 8 )(R 9 )] p - is defined as follows. Here, M 2 These are C, Si, Ge, Sn, and R 8 and R 9 These groups may be the same or different, and these groups are H, C1-C 20 Alkyl alkyl groups, C6-C 14 Aryl group, C1~C 10 Alkoxy group, C2~C 10 Alkenyl group, C7~C 20 Aryl group-substituted alkyl groups, C7~C 20 Alkyl-substituted aryl group, C6~C 10 Phenolic group, C1-C 10 Fluoroalkyl groups, C6-C 10 Aryl halide group, C2~C 10Alkynyl group, -SiR 7 3. A halogen, or a five- or six-membered heteroaromatic radical (containing one or more heteroatoms), and one or more rings formed by bonding them together with atoms, where p is 1, 2, or 3. The bridging group Y as defined in US5739366 is a divalent C1-C 20 Hydrocarbon group, divalent C1-C 20 Halide hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, 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 H, halogen atoms, C1-C 20 Hydrocarbon group, divalent C1-C 20 It is specified as a halogenated hydrocarbon group. In US6218558, US6252097B1 and US6255515B1, filed by Nippon Polychem Co., Ltd., the benzene ring in the indenyl ring is extended to a seven-membered ring, and the corresponding crosslinking group Q is a divalent C1-C 20 Hydrocarbon group, divalent C1-C 20 Halide hydrocarbon group, C1~C 20 hydrocarbon group or C1-C 20 Defined as a silicene group, oligosilylene group, or germylene group containing a halogenated hydrocarbon group, the group links two five-membered rings. Crosslinking group R as defined in US6444606B1, US7342078B2 and US2003 / 0149199A1 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 )-,-M 2 (R 10 )(R11 )-,-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 And,

[0010] Here, R 10 and R 11 These may be the same or different, and these groups may be H, a halogen atom, or C1-C 40 It is a group, for example C1~C 20 Alkyl alkyl groups, C1-C 10 Fluoroalkyl groups, C1-C 10 Alkoxy group, C6~C 14 Aryl group, C6~C 10 Fluoroaryl group, C6~C 10 Phenolic group, C2~C 10 Alkenyl group, C7~C 40 Aryl group-substituted alkyl groups, C7~C 40 Alkyl-substituted aryl group, C8~C 40 Aryl group-substituted alkenyl group, or R 10 and R 11It is bonded by atoms as one or more rings, M 2 These are Si, Ge, and Sn.

[0011] The crosslinking group attaches to two cyclopentadienyl, indenyl, or fluorenyl groups, meaning that the steric space is limited for these two groups. Such crosslinking enhances the rigidity of the ligand structure, which is important for forming catalysts with racemic characteristics. Racemic catalysts can effectively control chain extension by the stereoenometric sites of propylene, enabling the production of metallocene polypropylenes with high isotacticity.

[0012] Although many crosslinked metallocene catalysts have already been reported, there are still not many metallocene catalysts that have industrial application or future application potential. This is because industrial application requires very high isotacticity of metallocene polypropylene. For example, metallocene polypropylene manufactured by some companies cannot be used in resin products unless its isotacticity [mmmm] is greater than 97%. Polypropylene products in China are basically manufactured using conventional Natta-type catalysts, and although some catalysts have simple metallocene compound components added, the complete use of metallocene compounds as catalysts has not been reported, and theoretical and technical difficulties still remain in this regard.

[0013] Chinese polypropylene products are basically manufactured using conventional loaded Ziegler-Natta catalysts, and there are very few reports of using cross-linked bifunctional metallocene catalysts to control and produce polypropylene with high isotacticity. This is because technical difficulties still exist in this regard.

[0014] [Summary of the Invention] The first technical problem that the present invention aims to solve is to provide a novel metallocene compound, taking into account the technical problem that conventional metallocene catalysts do not have sufficiently high activity. The group connected to the bridging atom of the metallocene compound is a group substituted with an amine group and / or a group substituted with a metallocene group and / or a substituted metallocene group. Due to this special structure, the metallocene catalyst containing the metallocene compound has high catalytic activity and can synthesize metallocene polypropylene with high isotacticity.

[0015] The second technical problem that this invention aims to solve is to provide a manufacturing method applicable to metallocene compounds that solve the first technical problem.

[0016] The third technical problem that the present invention aims to solve is to provide a catalyst that employs a metallocene compound related to the first technical problem described above.

[0017] The fourth technical problem that the present invention aims to solve is to provide a manufacturing method suitable for a catalyst that solves the third technical problem described above.

[0018] The fifth technical problem that the present invention aims to solve is to provide an application for a metallocene compound that solves the first technical problem or a catalyst that solves the third technical problem.

[0019] To solve the first technical problem described above, the technical solutions employed by the present invention are as follows.

[0020] It is a metallocene compound, and its structure is as shown in formula (I),

[0021] [ka]

[0022] In equation (I), R I and R IIThey are the same or different, and R I and R II At least one of them is substituted with an amine group C1-C 20 hydrocarbon group, C1~C 20 Halide hydrocarbon group, C1~C 20 Alkoxy groups and C6-C 20 Selected from phenol groups, and / or R I and R II At least one of them is a C1-C1 substituted with a metallocene group. 20 hydrocarbon group, C1~C 20 Halide hydrocarbon group, C1~C 20 Alkoxy groups and C6-C 20 Selected from phenol groups, and / or R I and R II At least one of them is C1~C 20 hydrocarbon group, C1~C 20 Halide hydrocarbon group, C1~C 20 Alkoxy groups and C6-C 20 Selected from metallocene groups substituted with phenol groups, Z is selected from carbon, silicon, germanium, and tin. Cp III R is a cyclopentadienyl group, indenyl group, or fluorenyl group with or without substituents, as shown in formula (II), i , R ii , R iii These are the substituents on the corresponding ring,

[0023] [ka]

[0024] R i , R ii and R iii C1-C1 are the same or different, and each independently contains hydrogen and a straight or branched chain, saturated or unsaturated, heteroatoms or heteroatoms. 20 Selected from hydrocarbons, E is NR iv or PRiv And, R iv C1-C atoms containing hydrogen and straight or branched chains, saturated or unsaturated, heteroatoms, or non-heteroatom-containing C1-C atoms. 20 Selected from hydrocarbon groups, M is selected from the IVB group metals. L IV and L V C1-C1 are the same or different, and each independently contains hydrogen and a straight or branched chain, saturated or unsaturated, heteroatoms or heteroatoms. 20 Selected from hydrocarbons, n is either 1 or 2.

[0025] According to the present invention, when n is equal to 1, Cp III means any one of the above cyclopentadienyl group, indenyl group, or fluorenyl group. When n is equal to 2, Cp III This means two of the above cyclopentadienyl, indenyl, or fluorenyl groups, or any two of the cyclopentadienyl, indenyl, or fluorenyl groups. When n is 2, two Cp III The basis may be the same, but it can also be quite different.

[0026] According to a preferred embodiment of the present invention, the amine group is as shown in formula (III),

[0027] [ka]

[0028] In equation (III), R a and R b They are the same or different, and each independently consists of hydrogen, C1-C6 alkyl groups, and C6-C 18 Aryl group, C7~C 20 Arylalkyl groups and C7-C 20 Selected from alkylaryl groups, preferably C1-C6 alkyl groups, C6-C 12 Aryl group and C7~C10 The material is an arylalkyl group, and more preferably a C1-C4 alkyl group, a phenyl group, and a C7-C9 arylalkyl group.

[0029] According to a preferred embodiment of the present invention, the metal in the metallocene group is Fe, and preferably the metallocene group is a ferrocene group.

[0030] According to a preferred embodiment of the present invention, in formula (I), R I and R II They are the same or different, and R I and R II At least one of them is substituted with an amine group C1-C 10 hydrocarbon group, C1~C 10 Halide hydrocarbon group, C1~C 10 Alkoxy groups and C6-C 10 Selected from phenol groups, and / or R I and R II At least one of them is a C1-C1 substituted with a metallocene group. 10 hydrocarbon group, C1~C 10 Halide hydrocarbon group, C1~C 10 Alkoxy groups and C6-C 10 Selected from phenol groups, and / or R I and R II At least one of them is C1~C 10 hydrocarbon group, C1~C 10 Halide hydrocarbon group, C1~C 10 Alkoxy groups and C6-C 10 Selected from metallocene groups substituted with phenol groups.

[0031] According to a preferred embodiment of the present invention, in formula (I), R I and R II They are the same or different, and R I and R II At least one of these is selected from C1-C6 hydrocarbon groups, C1-C6 halogenated hydrocarbon groups, C1-C6 alkoxy groups and C6-C8 phenol groups substituted with an amine group, and / or RI and R II At least one of these is selected from a metallocene-substituted C1-C6 hydrocarbon group, a C1-C6 halogenated hydrocarbon group, a C1-C6 alkoxy group, and a C6-C8 phenol group, and / or R I and R II At least one of these is selected from metallocene groups substituted with C1-C6 hydrocarbon groups, C1-C6 halogenated hydrocarbon groups, C1-C6 alkoxy groups, and C6-C8 phenol groups.

[0032] According to a preferred embodiment of the present invention, in formula (I), R I and R II They are the same or different, and R I and R II At least one of these is selected from C1-C6 hydrocarbon groups substituted with an amine group, and / or R I and R II At least one of these is selected from C1-C6 hydrocarbon groups substituted with a metallocene group, and / or R I and R II At least one of these is selected from metallocene groups substituted with C1-C6 hydrocarbon groups.

[0033] According to a preferred embodiment of the present invention, in formula (I), R I and R II They are the same or different, and R I and R II At least one of them is selected from a C1-C6 linear alkyl group substituted with an amine group, and / or R I and R II At least one of them is selected from a C1-C6 linear alkyl group substituted with a metallocene group, and / or R I and R II At least one of these is selected from metallocene groups substituted with C1-C6 linear alkyl groups.

[0034] According to a preferred embodiment of the present invention, in formula (I), R I and R IIThey are the same or different, and R I and R II At least one of them is selected from C1-C4 linear alkyl groups substituted with an amine group, and / or R I and R II At least one of them is selected from a C1-C4 linear alkyl group substituted with a metallocene group, and / or R I and R II At least one of these is selected from metallocene groups substituted with C1-C4 linear alkyl groups.

[0035] According to a preferred embodiment of the present invention, R I and R II If only one of the groups is selected from the above-defined groups, the other group is C1~C 20 hydrocarbon group, C1~C 20 Halide hydrocarbon group, C1~C 20 Alkoxy groups and C6-C 20 A phenol group may be selected, preferably C1-C 10 hydrocarbon group, C1~C 10 Halide hydrocarbon group, C1~C 10 Alkoxy groups and C6-C 10 The group is a phenol group, more preferably a C1-C6 hydrocarbon group, a C1-C6 halogenated hydrocarbon group, a C1-C6 alkoxy group, and a C6-C8 phenol group, and even more preferably a C1-C6 hydrocarbon group.

[0036] According to the present invention, R i , R ii , R iii Cp represents the corresponding ring substituent in the above molecular formula. III If is a cyclopentadienyl group, i It can be substituted and connected one or four times independently at any one, two, three, or all four positions out of the four positions. III If R is an indenyl group, iR can be independently substituted and connected at any one of two positions in the five-membered ring, or at any two positions without selection, and R ii R can be substituted with one or four elements at any one, two, three, or all four positions of the six-membered ring, independently of each other. iii If the benzene ring on which it is located is part of the indenyl ring, then the definition is R ii It is similar to Cp. III If R is a fluorenyl group, ii , R iii Each of the two six-membered rings can be independently substituted with up to one or four elements at any one, two, three, or all four positions of each of the four positions. i , R ii , R iii Each is independently a hydrogen atom, a straight chain, or a branched chain of C1-C atoms. 20 Alkyl alkyl groups, C3-C 20 Cycloalkyl groups, C6-C 20 Aryl group, C7~C 20 Alkylaryl group or C7~C 20 This refers to arylalkyl groups, where these groups optionally contain one or more heteroatoms and may be saturated or unsaturated. i , R ii , R iii The intervening rings can form saturated or unsaturated ring groups, and these groups optionally contain one or more heteroatoms.

[0037] According to a preferred embodiment of the present invention, in formula (II), R i , R ii and R iii They are either the same or different, and each is independently hydrogen, C1~C 20 hydrocarbon group, C1~C 20 Alkyl halogens, C6-C 20 Aryl group, C6~C 20 Aryl halide group, C7~C 40 Arylalkyl groups, C7-C 40 Alkylaryl group, C3~C 20Cycloalkyl groups, C3-C 20 Heterocycloalkyl groups, C2-C 20 Alkenyl group, C2~C 20 Alkynyl group, C1~C 20 Alkoxy group, C6~C 20 Phenolic group, C1-C 20 The group is selected from amine groups and groups containing heteroatoms from groups 13 to 17.

[0038] According to a preferred embodiment of the present invention, in formula (II), R i , R ii and R iii They are either the same or different, and each is independently hydrogen, C1~C 10 hydrocarbon group, C1~C 10 Alkyl halogens, C6-C 10 Aryl group, C6~C 10 Aryl halide group, C7~C 20 Arylalkyl groups, C7-C 20 Alkylaryl group, C3~C 10 Cycloalkyl groups, C3-C 10 Heterocycloalkyl groups, C2-C 10 Alkenyl group, C2~C 10 Alkynyl group, C1~C 10 Alkoxy group, C6~C 10 Phenolic group, C1-C 10 The group is selected from amine groups and groups containing heteroatoms from groups 13 to 17.

[0039] According to a preferred embodiment of the present invention, in formula (II), R i , R ii and R iii They are the same or different, and each independently consists of hydrogen, C1-C6 hydrocarbon groups, C1-C6 alkyl halides, C6-C6 aryl groups, C6-C6 aryl halides, and C7-C 10 Arylalkyl groups, C7-C 10The group is selected from alkylaryl groups, C3-C6 cycloalkyl groups, C3-C6 heterocycloalkyl groups, C2-C6 alkenyl groups, C2-C6 alkynyl groups, C1-C6 alkoxy groups, C6-C6 phenol groups, C1-C6 amine groups, and groups containing heteroatoms from groups 13 to 17.

[0040] According to a preferred embodiment of the present invention, in formula (I), R iv C1-C atoms containing hydrogen and straight or branched chains, saturated or unsaturated, heteroatoms, or non-heteroatom-containing C1-C atoms. 10 Selected from hydrocarbon groups.

[0041] According to a preferred embodiment of the present invention, in formula (I), R iv This is selected from hydrogen and C1-C6 hydrocarbon groups that are linear or branched, saturated or unsaturated, and contain or do not contain heteroatoms.

[0042] According to a preferred embodiment of the present invention, in formula (I), M is selected from Ti, Zr, and Hf.

[0043] According to a preferred embodiment of the present invention, in formula (I), M is Zr.

[0044] According to a preferred embodiment of the present invention, L IV and L V These are the same and are selected from hydrogen, chlorine, methyl group, phenyl group, benzyl group, and dimethylamine group.

[0045] To solve the second technical problem described above, the technical solutions employed by the present invention are as follows.

[0046] Solution 1: A method for producing the above metallocene compound, If n=2, the manufacturing method is S1.H2(Cp III ) is reacted with an alkali metal organic compound to obtain the corresponding [H(Cp III )] -To produce alkali metal salts, S2.[H(Cp III )] - Alkali metal salts R I R II R reacts with ZX2 I R II Z[H(Cp III To generate )2, S3.R I R II Z[H(Cp III )2 is reacted with an alkali metal organic compound to obtain the corresponding R I R II Z(Cp III )2 2- To produce alkali metal salts, S4.R I R II Z(Cp III )2 2- Alkali metal salt x 2 ml IV L V And a salt removal reaction occurs, R I R II Z(Cp III ) 2ML IV L V To see, including, If n=1, the manufacturing method is S1.H2(Cp III ) and H2(E) are reacted with alkali metal organic compounds to obtain the corresponding [H(Cp III )] - Alkali metal salts and [H(E)] - To produce alkali metal salts, S2.[H(Cp III )] - Alkali metal salts and [H(E)] - Alkali metal salts R I R II R reacts with ZX2 I R II Z[H(Cp III To generate )][H(E), S3.R I R II Z[H(Cp III ) [H(E)] reacts with alkali metal organic compounds to produce the corresponding RI R II Z(Cp III )(E) 2- To produce alkali metal salts, S4.R I R II Z(Cp III )(E) 2- Alkali metal salt x 2 ml IV L V And a salt removal reaction occurs, R I R II Z(Cp III )(E)ML IV L V To obtain, including, Here, X is selected from Cl, Br, and I. 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- There is no need to separate alkali metal salts, X2ML IV L V This directly causes a salt removal reaction.

[0047] Solution 2: A method for producing the above metallocene compound, Precursor R I HZ(Cp III ) n (E) 2-n ML IV L V and R II The process includes producing the product by performing a Z hydrogenation reaction using a precursor. Here, the R II The precursor is a multiple bond-containing molecule, preferably selected from organic multiple bond molecules, CO, and CO2, where the multiple bond is selected from elements of group 13 to 16 of the same or different atoms, preferably C=C, C≡C, C=N, C≡N, C=O, C≡P, N=N, C=S, C=C=C, C=C=N, C=C=O, and N=C=N bonds.

[0048] According to the present invention, both Solution 1 and Solution 2 can produce the above-mentioned metallocene compound.

[0049] According to a preferred embodiment of the present invention, the metallocene compound is produced by solution 2. That 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 These compounds are produced by a ZH addition reaction with a multibond-containing molecule. Collins reported a stepwise synthesis method for MeHZ(Cp)2Zr(NMe2)2 and MeHZ(Ind)2Zr(NMe2)2 (Macromolecules 2001, 34, 3120). Specifically, the dimetallocene ligands MeHZ(CpH)2 and MeHZ(IndH)2 are produced, respectively, and then reacted with Zr(NMe2)4 to produce MeHZ(Cp)2Zr(NMe2)2 and MeHZ(Ind)2Zr(NMe2)2. This method is similar to the synthesis methods for demetallocene rings or nonmetallocene compound protons described in the background art. These two compounds react with excess Me3ZCl to obtain the compounds MeHZ(Cp)2ZrCl2 and MeHZ(Ind)2ZrCl2, respectively.

[0050] 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 Regarding the production of [product name], the technical solution employed by the present invention may use such methods, or the salt removal method mentioned in the background art may be employed, but preferably the one-pot production method is employed. The present invention provides a specific embodiment of the one-pot method, and the implementation process of the one-pot method is not changed when the selected raw materials are changed.

[0051] If n=2, R I Select HZX2 and add 2 moles of H(Cp) III ) react with alkali metal salts (H(Cp III ) If there are two different metallocene groups, then each is in the amount of 1 mole), H(Cp III Alkali metal salts are metallocene ligands H2(Cp III It is obtained by reacting ) with an equal amount of alkali metal organic compound, the alkali metal organic compound is selected from metal hydrides, alkyl metals, alkenyl metals, aromatic metals, and amine metals, and is preferably an alkyl metal. The alkali metal is selected from Li, Na, and K, and is preferably Li. X is selected from Cl, Br, and I, and is 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, and there are two ways to solve this.

[0052] a)L viii L viv ML IV L V It reacts with the stable small molecule HL viii or HL viv Remove and reattach R I HZ(Cp III ) 2ML IV L V Obtained, L viii and L viv The group that leaves the body is the same or different group, and is selected from hydrogen, alkyl groups, aryl groups, and amine groups, preferably two identical methyl groups, phenyl groups, and dimethylamine groups.

[0053] b) Reacts with 2 molars of an alkali metal organic compound to produce an alkali metal salt, the definition of the alkali metal organic compound is the same as above. Furthermore, X2ML IV L V Then the salt removal reaction is carried out R I HZ(Cp III ) 2ML IV L V The result is obtained, and the definition of X is the same as above.

[0054] If n=1, R I Select HZX2 to add 1 mole of H(Cp) III ) React with an alkali metal salt and 1 mole of H(E) with an alkali metal salt, and H(Cp III The production of alkali metal salts is the same as above; alkali metal salts of H(E) are produced by reacting H2(E) with an equal amount of alkali metal organic compound, and the definition of alkali metal organic compound is the same as above. The generated R I HZ[H(Cp III )][H(E)] does not need to be separated and is used directly in the next reaction, and there are two ways to solve this.

[0055] a)L viii L viv ML IV L V It reacts with the stable small molecule HL viii or HL viv Remove and reattach R I HZ(Cp III )(E)ML IV L V Obtained, L viii and L viv The definition is the same as above.

[0056] b) Reacts with 2 molars of an alkali metal organic compound to produce an alkali metal salt, the definition of the alkali metal organic compound is the same as above. Furthermore, X2ML IV L V Then the salt removal reaction is carried out R I HZ(Cp III )(E)ML IV L VThe result is obtained, and the definition of X is the same as above.

[0057] R II Select HZX2 and R II HZ(Cp III ) n (E) 2-n ML IV L V Either manufacture H2ZX2 or select H2Z(Cp III ) n (E) 2-n ML IV L V Manufacturing this is similar to the solution described above.

[0058] 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 In the manufacturing process, the reaction is carried out in an aprotic solvent, which is selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, preferably toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, trichloromethane, tetrahydrofuran, diethyl ether and dioxane. Here, 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(CpIII )][H(E)] or H2Z[H(Cp III The reaction between [H(E)] and alkali metal organic compounds is carried out at temperatures of -60 to 140°C, with a preferred temperature range of -20 to 110°C. The reaction time is greater than 0.016 h, with a preferred reaction time range of 2 to 100 h. I HZX2, R II HZX2, H2ZX2 and H(Cp III ) Reaction with H(E) alkali metal salts, and X2ML IV L V and 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 The reaction with alkali metal salts is carried out at temperatures of -75 to 100°C, with a preferred temperature range of -75 to 60°C. The reaction time is greater than 0.1 hours, with a preferred reaction time range of 6 to 100 hours. 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)], H2Z[H(Cp III Each of )][H(E) is L viii L viv ML IV L V The reaction to desorb stable small molecules is carried out at temperatures of 0 to 160°C, with a preferred temperature range of 20 to 140°C. The reaction time is greater than 0.1 hours, with a preferred reaction time range of 2 to 100 hours.

[0059] Further technical solutions provided by the present invention include precursor R IHZ(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 The ZH is produced by performing a ZH addition reaction with a multiple bond-containing molecule (I). In these multiple bond molecules, the multiple bond is selected from multiple bonds composed of elements from groups 13 to 16, and may be composed of homogeneous or heterogeneous atoms, preferably C=C, C≡C, C=N, C≡N, C=O, C≡P, N=N, C=S, C=C=C, C=C=N, C=C=O, N=C=N. The ZH addition reaction requires catalytic oxidation, and the catalyst is selected from transition metal catalysts and Lewis acid catalysts, preferably platinum catalysts in transition metals and B(C6F5)3 catalysts in Lewis acid. To better achieve the object of the present invention, it is also preferable that the above precursor contains L IV and L V A catalyst is required that does not act with or does not affect the reaction between ZH and the multiple bond. This requires a catalyst and L in the above precursor. IV and L V When L acts to affect the addition reaction between ZH and the multiple bond, such L IV and L V This means that the group needs to be converted through a group transformation reaction using the manufactured related compound, so as not to affect the reaction between ZH and the multiple bond. To illustrate with an example, L IV and L V If the group is a methyl group, the B(C6F5)3 catalyst complexes with the methyl group to form [MeB(C6F5)3] - It forms and loses its catalytic effect. Then L IV and L V It needs to be converted to NMe2 or another non-reactive group.

[0060] 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 The reaction between ZH and the multiple bonded molecules takes place in an aprotic solvent, which is selected from linear or branched alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, ethers, and cyclic ethers, preferably toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, trichloromethane, tetrahydrofuran, diethyl ether, and dioxane. The amount of catalyst used in the reaction is 0.00001 to 50% of the total mass percentage of the reactants, with a preferred ratio of 0.01 to 20%. 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 0.1 hours, with a preferred reaction time range of 2 to 50 hours. The target product (I) is separated or purified by recrystallization.

[0061] According to the present invention, "Z" is preferably silicon.

[0062] According to a preferred embodiment of the present invention, the Z hydrogenation reaction is carried out in the presence of a catalyst, the catalyst being selected from transition metal catalysts and Lewis acid catalysts, preferably platinum catalysts in transition metals and B(C6F5)3 catalysts in Lewis acid.

[0063] 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, with a preferred ratio of 0.01 to 20%.

[0064] 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.

[0065] According to a preferred embodiment of the present invention, the reaction time for the Z hydrogenation reaction is greater than 0.1 hours, and preferably 2 to 50 hours.

[0066] According to a preferred embodiment of the present invention, the obtained precursor is separated or purified by recrystallization, the solvent for recrystallization being an aprotic solvent, preferably selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, and more preferably selected from toluene, xylene, hexane, heptane, cyclohexane and methylcyclohexane.

[0067] According to a preferred embodiment of the present invention, the precursor R I HZ(Cp III ) n (E) 2-n ML IV L V It is produced by a one-pot chemical reaction.

[0068] According to a preferred embodiment of the present invention, when n=2, the precursor R I HZ(Cp III ) n (E) 2-n ML IV L V The manufacturing method is Step (1), H2(Cp III ) is reacted with an alkali metal organic compound to obtain the corresponding [H(Cp III )] - To produce alkali metal salts, Step (2), [H(Cp III )] - Alkali metal salts R I R reacts with HZX2 I HZ[H(Cp III To generate )2, Step (3), RI HZ[H(Cp III )2 does not need to be separated, directly L viii L viv ML IV L V It reacts with the stable small molecule L viii or L viv Detach the precursor R I HZ(Cp III ) 2ML IV L V To obtain and / or, R I HZ[H(Cp III )]2 does not need to be separated, and is directly reacted with an alkali metal organic compound to produce an alkali metal salt, and the resulting alkali metal salt is further processed into X2ML IV L V The salt removal reaction is carried out, and the precursor R I HZ(Cp III ) 2ML IV L V To see, including, When n=1, the precursor R I HZ(Cp III ) n (E) 2-n ML IV L V The manufacturing method is Step (1), H2(Cp III ) and H2(E) are reacted with alkali metal organic compounds to obtain the corresponding [H(Cp III )] - and [[H(E)] - To produce alkali metal salts, Step (2), [H(Cp III )] - and [H(E)] - Alkali metal salts R I R reacts with HZX2 I HZ[H(Cp III To generate )][H(E), Step (3), R I HZ[H(Cp III There is no need to separate )][H(E) and L viii L viv ML IVL V It reacts directly with the stable small molecule L viii or L viv Detach the precursor R I HZCp III EML IV L V To obtain and / or, R I HZ[H(Cp III There is no need to separate [H(E)], and alkali metal salts are produced by directly reacting them with alkali metal organic compounds. The resulting alkali metal salts can then be further processed into X2ML. IV L V The salt removal reaction is carried out, and the precursor R I HZCp III EML IV L V To see, including, Here, X is selected from Cl, Br, and I.

[0069] According to the present invention, when employing the one-pot method, R I is precursor R II HZ(Cp III ) n (E) 2-n ML IV L V It is formed by an addition reaction between the ZH bond inside and the multiple bond in the multiple bond-containing molecule, R II is precursor R I HZ(Cp III ) n (E) 2-n ML IV L V It is formed by an addition reaction between the ZH bond in the molecule and the multiple bond in the molecule containing multiple bonds, or R I and R II All of these are precursor H2Z (Cp III ) n (E) 2-n ML IV L V It is formed by an addition reaction between the ZH bond in the molecule and the multiple bond in the multiple bond-containing molecule, and the multiple bond molecule is an organic multiple bond molecule, CO, or CO2, preferably an organic multiple bond molecule. This results in R I and R IIThey may be the same or they may be different.

[0070] 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.

[0071] In a preferred embodiment of the present invention, in each step, the reaction materials are mixed under conditions of -100°C to -20°C, preferably -85°C to -10°C, and the mixed reaction materials are reacted at 10°C to 50°C, preferably 20°C to 35°C for 1 hour to 100 hours, preferably 5 hours to 50 hours.

[0072] According to preferred embodiments of the present invention, in each step, the reaction is carried out in an aprotic solvent, the aprotic solvent being selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds, and preferably from toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, trichloromethane, tetrahydrofuran, ethyl ether and dioxane.

[0073] According to a preferred embodiment of the present invention, the alkali metal organic compound is selected from metal hydrides, alkyl metals, alkenyl metals, aromatic metals, and amine metals, and is preferably an alkyl metal, and more preferably a C1-C6 alkyl metal.

[0074] According to a preferred embodiment of the present invention, the alkali metal is selected from Li, Na, and K, and is preferably Li.

[0075] To solve the third technical problem described above, the technical solutions employed by the present invention are as follows.

[0076] A catalyst for α-olefin polymerization reaction comprising the above-mentioned metallocene compound or a metallocene compound produced by the above-mentioned production method, a co-catalyst, and a support.

[0077] According to a preferred embodiment of the present invention, the co-catalyst is selected from a Lewis acid and an ionic compound containing a non-coordinating anion and a Lewis acid or Brønsted acid cation, preferably the Lewis acid includes alkylaluminum, alkylaluminoxane and organoborides, and / or the ionic compound containing the non-coordinating anion and the Lewis acid or Brønsted acid cation is selected from compounds containing a borate anion substituted with 1 to 4 perfluoroaryl groups.

[0078] According to preferred embodiments of the present invention, the alkylaluminum includes trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, triisohexylaluminum, tri-n-hexylaluminum, triisoheptylaluminum, tri-n-heptylaluminum, triisooctylaluminum, tri-n-octylaluminum, triisononylaluminum, tri-n-nonylaluminum, triisodecylaluminum and tri-n-decylaluminum, and / or the alkylaluminoxane includes methylaluminoxane, ethylaluminoxane and butyl-modified aluminoxane, and / or the organoboride includes trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and tris(2,4,6-trifluorophenyl)borane.

[0079] According to a preferred embodiment of the present invention, the alkylaluminum includes trimethylaluminum and triethylaluminum.

[0080] According to a preferred embodiment of the present invention, 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.

[0081] According to a preferred embodiment of the present invention, in the catalyst, the content of the metallocene compound is 0.001% to 10% by mass of element M, preferably 0.01% to 1% by mass, and / or the molar ratio of element Al in the co-catalyst to element M in the metallocene compound is (1 to 500):1, preferably (50 to 300):1.

[0082] According to a preferred embodiment of the present invention, the catalyst has an asymmetric structure. The asymmetric structure may be an asymmetric structure in multiple aspects, and it is the R in the metallocene compound. I and R II This may mean that the structure is asymmetric, or that the metallocene compound and the auxiliary agent act to form an asymmetric structure, or that after the metallocene compound and the auxiliary agent act, it is supported on a carrier, further enhancing the asymmetry.

[0083] To solve the fourth technical problem described above, the technical solutions employed by the present invention are as follows.

[0084] A method for producing the catalyst, comprising bonding the metallocene compound, the co-catalyst, and the support under the action of a solvent to form the catalyst.

[0085] According to a preferred embodiment of the present invention, the bonding conditions include a bonding temperature of -40°C to 200°C, preferably 40°C to 120°C, and a bonding time greater than 0.016h, preferably 2h to 100h.

[0086] According to a preferred embodiment of the present invention, the solvent is selected from linear hydrocarbon compounds, branched hydrocarbon compounds, cyclic saturated hydrocarbon compounds and aromatic hydrocarbon compounds, and is preferably toluene, xylene, n-butane, n-pentane, isopentane, neopentane, cyclopentane, methylcyclopentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, petroleum ether, isoheptane, and neoheptane.

[0087] According to a preferred embodiment of the present invention, the method for producing the catalyst is as follows: i) Mix the co-catalyst, the support and the solvent to obtain mixture A. ii) Mixing mixture A and the metallocene compound to obtain mixture B, preferably by first mixing the metallocene compound with a solvent and then mixing it with mixture A. iii) The method includes separating a solid from the mixture B, drying the solid, and obtaining the catalyst.

[0088] According to a preferred embodiment of the present invention, in step (i), the carrier is subjected to a calcination treatment, 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.

[0089] According to a preferred embodiment of the present invention, the mixture A is heat-treated, preferably the conditions for the heat treatment include a heating temperature of 30°C to 110°C and a heating time of 0.1h to 100h.

[0090] According to a preferred embodiment of the present invention, in step (iii), the conditions for the drying treatment include a drying temperature of 30°C to 110°C and a drying time of 0.1h to 100h.

[0091] According to a preferred embodiment of the present invention, the solid is washed before the drying process, preferably using the solvent, and more preferably washing until the solvent after washing does not contain metal ions.

[0092] To solve the fifth technical problem described above, the technical solutions employed by the present invention are as follows.

[0093] Application of the above metallocene compound or a metallocene compound produced by the above production method or the above catalyst or a catalyst produced by the above production method in the field of α-olefin polymerization.

[0094] According to a preferred embodiment of the present invention, a polymerization reaction is carried out with α-olefin in the presence of the metallocene compound or a metallocene compound produced by the above production method or the catalyst or a catalyst produced by the above production method to obtain poly-α-olefin.

[0095] According to a preferred embodiment of the present invention, the polymerization reaction is carried out under conditions without a solvent.

[0096] According to a preferred embodiment of the present invention, the conditions for 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.

[0097] According to a preferred embodiment of the present invention, the amount of metallocene catalyst or metallocene catalyst system used per gram of α-olefin is 0.001 mg to 1000 mg, preferably 0.01 mg to 200 mg, and more preferably 0.1 mg to 20 mg.

[0098] According to a preferred embodiment of the present invention, the α-olefin is C2-C 20 It contains α-olefins, preferably C2-C 14The α-olefin is more preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene, and more preferably 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene.

[0099] 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 carried out using propylene and hydrogen gas as raw materials (such a bulk polymerization reaction can be carried out in a kettle reactor and is also suitable for a tubular reactor. It may be carried out intermittently or continuously), and the amount of hydrogen gas used may be 0 to 0.10 g / g of propylene, preferably 0.00001 to 0.10 g / g of propylene. Furthermore, an impurity removal agent can be used when polymerizing propylene. The impurity removal agent is a substance commonly used in this field, and the specific amount used may be 0 to 100 mmol / g of propylene, preferably 0.001 to 10 mmol / g of propylene.

[0100] 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 carried out, the reaction temperature is 0 to 200°C, preferably 20 to 140°C, and / or the reaction time is 0.016 to 60 h, preferably 0.1 to 20 h, and / or the ethylene pressure is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and / or the amount of catalyst used is 0.00001 to 100 mg / g of ethylene, and / or the amount of impurity removal agent used is 0 to 100 mmol / g of ethylene, and / or the amount of hydrogen gas used is 0 to 0.01 g / g of ethylene.

[0101] According to some embodiments of the present invention, the impurity remover is selected from alkylaluminum compounds, aromatic aluminum compounds, aluminoxane compounds, boron hydride compounds, alkylmagnesium compounds, aromatic magnesium compounds, alkylzinc compounds, aromatic zinc compounds, alkyllithium compounds, aromatic lithium compounds, alkylsodium compounds, aromatic sodium compounds, alkylpotassium compounds and aromatic potassium compounds, and is preferably selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and modified aluminoxane, alkylaluminum halide, dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, methyllithium, n-butyllithium and t-butyllithium.

[0102] In the present invention, the term "hydrocarbon group" may refer to alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkynyl groups, alkenyl groups, and the like.

[0103] In the present invention, the term "heteroatom" can mean heteroatoms such as oxygen, sulfur, nitrogen, and phosphorus.

[0104] In the present invention, the term "substitution" can mean substitution with a substituent. The substituent may be selected from halogens, noncarbon oxoacid groups and their derivatives, and optionally substituted alkyl groups, aralkyl groups and aryl groups, for example, groups substituted with alkyl groups, aryl groups, amino groups, hydroxyl groups, alkoxy groups, carbonyl groups, oxa, carboxyl groups, thio, thiooxoacids and halogeno groups and combinations thereof.

[0105] In this invention, the term "one-pot method" can refer to a series of multi-step synthesis reactions carried out in the same reactor.

[0106] In this invention, "Me" means a methyl group, "Et" means an ethyl group, "iPr" means an isopropyl group, "tBu" means a t-butyl group, "iBu" means an isobutyl group, "iPr" means an isopropyl group, "Ph" means a phenyl group, "Fc" means CpFe(C5H4), and "Flu" means a fluorenyl group.

[0107] In this invention, "Tol" means toluene.

[0108] The beneficial effects of the present invention are at least as follows:

[0109] 1) At least one of the two different groups on the crosslinking atom of the metallocene compound employed in the present invention is a group substituted with an amine group and / or a group substituted with metallocene and / or a substituted metallocene group, thereby promoting the generation of a racemic metallocene catalyst, which, when combined with a co-catalyst and support, enables chain extension by stereoenograph site control of olefins, such as propylene and ethylene, and produces metallocene polypropylene or metallocene polyethylene with high isotacticity.

[0110] 2) The method for producing metallocene compounds provided by the present invention effectively performs group transformation of crosslinking atoms, enabling the production of crosslinking metallocene compounds with diverse structures and compositions. The crosslinking metallocene compound obtained after the hydrogenation reaction of the crosslinking atoms can be combined with a co-catalyst and a support to form a metallocene catalyst, which has good thermal stability and catalytic activity and can carry out polymerization reactions of alpha-olefins such as ethylene or propylene.

[0111] [Modes for carrying out the invention] The present invention will be further described below with reference to examples.

[0112] In the embodiments described below, unless otherwise specified, the aluminum / zirconium ratio is the molar ratio of aluminum to zirconium.

[0113] In this invention, unless otherwise specified, the Al / Zr ratio refers to the molar ratio of Al to Zr.

[0114] In this invention, unless otherwise specified, "%" means mass percentage.

[0115] In the present invention, the formula for calculating polymerization activity is as follows:

[0116] Polymerization activity = Mass of polymerization product / (Polymerization time × Amount of catalyst used × Zirconium content)

[0117] (A. Production of metallocene compounds) [Synthesis Example 1] Preparation of the metallocene compound shown in Formula 1 Weigh out 40 mmol of 4-phenyl-2-methylindene and dissolve it in 200 mL of Et2O. Cool to -78°C and slowly add 40 mmol of a 2.4 M hexane solution of n-butyllithium to it dropwise, completing the addition over 15 minutes. Allow to return to room temperature naturally while stirring, and stir at room temperature for a further 12 hours to obtain a solution of the indenyl lithium compound.

[0118] 20 mmol of Me(PhMeNH2CH2CH2C)SiCl2 was weighed out and dissolved in 100 mL of n-hexane. The mixture was cooled to -78°C, and the solution of the prepared indenyl lithium compound was slowly added dropwise, completing the addition over 30 minutes. The mixture was allowed to rise naturally to room temperature while stirring, and then stirred at room temperature for a further 12 hours. The solution was filtered to remove insoluble matter, and the filtrate was passed through a silica gel column to obtain a yellow solution. The solvent was dried by suction to obtain the yellow compound Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H5)2, weighed in at a volume of 8.2 mmol and yielded in 41%.

[0119] Weigh out 5 mmol of Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H5)2, dissolve it in 100 mL of THF, cool to -78°C, and slowly add 10 mmol of a 2.4 M hexane solution of n-butyllithium to it, completing the addition over 15 minutes. Allow to return to room temperature naturally while stirring, and stir at room temperature for a further 12 hours to obtain a solution of silicon-bridged indenyl lithium compound.

[0120] 5 mmol of ZrCl4 is weighed out, 100 mL of THF is added, and the mixture is cooled to -78°C. The solution of the silicon-linked indenyl lithium compound is slowly added dropwise while stirring, and the addition is completed in over 15 minutes. The mixture is allowed to rise naturally to room temperature while stirring, and then stirred at room temperature for a further 12 hours. The mixture is filtered to remove insoluble matter, the filtrate is collected, the THF solvent is extracted from the filtrate, and the remaining solid is extracted with 100 mL of toluene. The extract is crystallized at -20°C to obtain the orange-red metallocene zirconium compound [Me(PhMeNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2]ZrCl2 shown in Formula 1, with a weighing of 1.2 mmol and a yield of 24%.

[0121] The method for producing the metallocene compounds of formulas 2 to 11 is similar, except that in the second step, instead of Me(PhMeNH2CH2CH2C)SiCl2, Me(Me2NH2CH2CH2CH2C)SiCl2, Me(Me2NH2CH2C)SiCl2, Me(Me2NH2CH2C)SiCl2, Me(Me2NH2CH2CH2C)SiCl2, Me(NH2Pr2NH2CH2CH2C)SiCl2, Me(iPr2NH2CH2CH2C)SiCl2, Me(iBuMeNH2CH2CH2C)SiCl2, Me(iBuE Using tNH2CH2CH2C)SiCl2, Me(iPrEtNH2CH2CH2C)SiCl2, and (Me2NH2CH2C)(iBuMeNH2CH2CH2C)SiCl2, the final metallocene zirconium compounds Me(PhMeNH2CH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Formula 2, weighing 1.0 mmol, yield 20%), Me(Me2NH2CH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Formula 3, weighing 1.4 mmol, yield 28%), and Me(Me2NH2CH2C) Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 4, weighing 1.2 mmol, yield 24%), Me(Me2NH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 5, weighing 1.0 mmol, yield 20%), Me(NH2Pr2NH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 6, weighing 1.3 mmol, yield 26%), Me(iPr2NH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 7, weighing 1.0 mmol, yield 20%), Me(iBuMeNH2CH2CH2C) The following compounds are obtained: Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 8, weighing 0.9 mmol, yield 18%), Me(iBuEtNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 9, weighing 0.8 mmol, yield 16%), Me(iPrEtNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 10, weighing 0.9 mmol, yield 18%), and (Me2NH2CH2C)(iBuMeNH2CH2CH2C)Si(4-Ph-2-MeC9H4)2ZrCl2 (Equation 11, weighing 0.6 mmol, yield 12%).

[0122] The methods for producing the metallocene compounds of formulas 12 to 14 are similar, except that instead of Me(PhMeNCH2CH2CH2)SiCl2 in the second step, Me[CpFe(C5H4)CH2CH2]SiCl2, Me[CpFe(C5H4)CH2CH2CH2]SiCl2, and Me[CpFe(C5H4)CH2]SiCl2 are used, and finally, the metallocene zirconium compounds Me[CpFe(C5H4)CH2]SiCl2 are produced. The following compounds are obtained: H4)CH2CH2]Si(4-Ph-2-MeC9H4)2ZrCl2 (Formula 12, weighing 1.0 mmol, yield 20%), Me[CpFe(C5H4)CH2CH2CH2]Si(4-Ph-2-MeC9H4)2ZrCl2 (Formula 13, weighing 1.3 mmol, yield 26%), and Me[CpFe(C5H4)CH2]Si(4-Ph-2-MeC9H4)2ZrCl2 (Formula 14, weighing 0.8 mmol, yield 16%).

[0123] The method for producing the metallocene compound of formula 15 is similar to this, except that 4-(4-t-butyl)phenyl-2-methylindene is used instead of 4-phenyl-2-methylindene in the first step, and at the same time, Me[CpFe(C5H4)CH2CH2]SiCl2 is used instead of Me(PhMeNCH2CH2CH2)SiCl2 in the second step, and finally the metallocene zirconium compound Me[CpFe(C5H4)CH2CH2]Si(4-(4-tBuC6H4)-2-MeC9H4)2ZrCl2 (formula 15, weigh 1.0 mmol, yield 20%) is obtained.

[0124] [Preparation of the precursor for synthesis example 2-12] (Preparation of MeHSi(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(MS-1), a hydrogen-based silicon-bridged bisindenyl zirconocene compound) 5.24 g of 2-methyl-7-p-tert-butylphenylindene (2.24 g, 20 mmol) is weighed out and dissolved in 80 mL of solvent. At -78°C, n-butyllithium (2.4 M, 8.5 mL, 20 mmol) is slowly added dropwise, and the mixture is allowed to react overnight while gradually returning to room temperature to obtain a wine-red solution. At -78°C, 1.04 mL of methyldichlorosilane (1.04 mL, 10 mmol) is slowly added dropwise, and the mixture is allowed to react for at least 8 hours while gradually returning to room temperature to obtain a yellow suspension. The yellow suspension is left at -78°C, and n-butyllithium (2.4 M, 8.5 mL, 20 mmol) is slowly added dropwise. After returning to room temperature, the mixture is stirred for 2 hours to obtain an orange turbidity. 2.33 g, 10 mmol of zirconium tetrachloride was taken from a glove box, placed in a vial, 40 mL of toluene was added, the nitrogen protection was removed, and the mixture was added to the yellow suspension at room temperature. The color gradually deepened from orange to brown-black, and the reaction was allowed to proceed for 1 day. The reaction mixture was filtered under nitrogen gas protection, the solvent was dried by suction from the resulting filtrate, and the mixture was washed with n-hexane, filtered, and dried by suction to obtain a yellow solid. The yellow solid was recrystallized in toluene at -20°C in a multi-step process to obtain rac-MS-11.76 g (24.2%), a racemic compound, and meso-MS-13.42 g (47.0%), a meso compound.

[0125] These two compounds are isomers and have the same elemental composition. Select one of them and perform elemental analysis to confirm its composition. The composition is C 41 H 48 Cl2SiZr (Mr=731.04): Theoretical values: C, 67.36; H, 6.62. Measured values: C, 67.54; H, 6.56.

[0126] [Synthesis Example 2] (Preparation of Me(Me2NCH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1a), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) Weigh out rac-MS-1 (1.45 g, 2 mmol) and dissolve it in Tol (100 mL) solvent. Add Me2NCH=CH2 (0.156 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-1a 1.36 g (85.2%), a yellow solid.

[0127] The composition is C 45 H 57 Cl2NSiZr(Mr=802.16): Theoretical values: C, 67.38; H, 7.16; N, 1.75. Measured values: C, 67.42; H, 7.19; N, 1.78.

[0128] [Synthesis Example 3] (Preparation of Me(Me2NCH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(meso-MS-1a), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Synthesis Example 2, except that meso-MS-1 (1.45 g, 2 mmol) is used instead of rac-MS-1, and finally, 1.4 g (87.7%) of meso-MS-1a, a yellow solid, is obtained.

[0129] Compound meso-MS-1 and the above-mentioned rac-MS-1 are isomers, and their compositions are also C 45 H 57 Cl2NSiZr(Mr=802.16): Theoretical values: C, 67.38; H, 7.16; N, 1.75. Measured values: C, 67.44; H, 7.18; N, 1.77.

[0130] [Synthesis Example 4] (Preparation of Me(PhMeNCH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1b), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Synthesis Example 2, except that PhMeNCH=CH2 (0.293 g, 2.2 mmol) is used instead of Me2NCH=CH2 to obtain rac-MS-1b 1.65 g (95.9%), which is a yellow solid.

[0131] The composition is C 50 H 59 Cl2NSiZr(Mr=864.23): Theoretical values: C, 69.49; H, 6.88; N, 1.62. Measured values: C, 69.45; H, 6.89; N, 1.65.

[0132] [Synthesis Example 5] (Preparation of Me(Me2NCH2CH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1c), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that Me2NCH=CH2 (0.187 g, 2.2 mmol) is used instead of Me2NCH=CH2, and finally rac-MS-1c 1.35 g (83.2%), which is a yellow solid, is obtained.

[0133] The composition is C 46 H 59 Cl2NSiZr(Mr=816.18): Theoretical values: C, 67.69; H, 7.29; N, 1.72. Measured values: C, 67.65; H, 7.30; N, 1.70.

[0134] [Synthesis Example 6] (Preparation of Me(PhMeNCH2CH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1d), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that PhMeNCH2CH=CH2 (0.324 g, 2.2 mmol) is used instead of Me2NCH=CH2, and finally rac-MS-1d 1.61 g (92.3%), which is a yellow solid, is obtained.

[0135] The composition is C51 H 61 Cl2NSiZr(Mr=878.25): Theoretical values: C, 69.75; H, 7.00; N, 1.59. Measured values: C, 69.78; H, 7.02; N, 1.60.

[0136] [Synthesis Example 7] (Preparation of Me(iPr2NCH2CH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1e), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that iPr2NCH2CH=CH2 (0.310 g, 2.2 mmol) is used instead of Me2NCH=CH2, and finally a yellow solid, rac-MS-1e, is obtained in 1.54 g (88.8%) form.

[0137] The composition is C 50 H 67 Cl2NSiZr(Mr=872.29): Theoretical values: C, 68.85; H, 7.74; N, 1.61. Measured values: C, 68.83; H, 7.71; N, 1.63.

[0138] [Synthesis Example 8] (Preparation of Me(iBuMeNCH2CH2CH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1f), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that iBuMeNCH2CH2CH=CH2 (0.310 g, 2.2 mmol) is used instead of Me2NCH=CH2, and finally a yellow solid, rac-MS-1f, is obtained in 1.57 g (90.62%) form.

[0139] The composition is C 50 H 67 Cl2NSiZr(Mr=872.29): Theoretical values: C, 68.85; H, 7.74; N, 1.61. Measured values: C, 68.82; H, 7.72; N, 1.63.

[0140] [Synthesis Example 9] (Preparation of Me(PhMeNCH2CH2CH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1g), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that PhMeNCH2CH2CH=CH2 (0.354 g, 2.2 mmol) is used instead of Me2NCH=CH2, and finally a yellow solid, rac-MS-1g 1.64 g (92.52%), is obtained.

[0141] The composition is C 52 H 63 Cl2NSiZr(Mr=892.28): Theoretical values: C, 70.00; H, 7.12; N, 1.57. Measured values: C, 70.04; H, 7.11; N, 1.59.

[0142] [Synthesis Example 10] (Preparation of Me(iPrEtNCH2CH2CH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1h), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that iPrEtNCH2CH2CH=CH2 (0.310 g, 2.2 mmol) is used instead of Me2NCH=CH2, and finally a yellow solid, rac-MS-1h, is obtained in 1.57 g (90.61%) form.

[0143] The composition is C 50 H 71 Cl2NSiZr(Mr=876.32): Theoretical values: C, 68.53; H, 8.17; N, 1.60. Measured values: C, 68.51; H, 8.18; N, 1.62.

[0144] [Synthesis Example 11] (Preparation of Me(FcCH=CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1i), a ferrocenyl-containing silicon-crosslinked bisindenyl zirconocene compound) The procedure is the same as in Example 1, except that FcC≡CH (0.420 g, 2 mmol) is used instead of Me2NCH=CH2, and finally, rac-MS-1i 1.72 g (91.98%), an orange-red solid, is obtained. In FcC≡CH, Fc=CpFe(C5H4).

[0145] The composition is C 53 H 58 Cl2FeSiZr (Mr=941.09): Theoretical values: C, 67.64; H, 6.21. Measured values: C, 67.71; H, 6.25.

[0146] [Synthesis Example 12] (Preparation of Me(FcCH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2ZrCl2(rac-MS-1j), a silicon-crosslinked bisindenyl zirconocene compound containing ferrocenealkyl) The procedure is the same as in Example 1, except that FcCH=CH2 (0.424 g, 2 mmol) is used instead of Me2NCH=CH2, and finally, rac-MS-1j 1.63 g (87.17%), an orange-red solid, is obtained. Of the FcCH=CH2, Fc=CpFe(C5H4).

[0147] The composition is C 53 H 60 Cl2FeSiZr (Mr=943.10): Theoretical values: C, 67.50; H, 6.41. Measured values: C, 67.53; H, 6.43.

[0148] [Preparation of precursors for synthesis examples 13 and 14] (Preparation of MeHSi(2-Me-7-p-tBuC6H4C9H4)2Zr(NMe2)2(rac-MS-2), a hydrogenated silicon-bridged bisindenyl zirconocene compound) 5.24 g of 2-methyl-7-p-tert-butylphenylindene (2.24 g, 20 mmol) is weighed out and dissolved in 160 mL of solvent. At -78°C, n-butyllithium (2.4 M, 8.5 mL, 20 mmol) is slowly added dropwise, and the mixture is allowed to react overnight while gradually returning to room temperature to obtain a wine-red solution. At -78°C, 1.04 mL of methyldichlorosilane (1.04 mL, 10 mmol) is slowly added dropwise, and the mixture is stirred for at least 8 hours while gradually returning to room temperature to obtain a yellow suspension. The solution is filtered to remove the LiCl precipitate and obtain a yellow solution. Tetramethylamine zirconium (2.68 g, 10 mmol) is added while stirring. The mixture is heated at 70-100°C for 12 hours. After cooling to room temperature, the volatile components are removed, and the remaining solid is recrystallized with toluene and hexane to obtain 4.83 g (64.9%) of rac-MS-2, an orange crystalline solid.

[0149] The composition is C 45 H 60 N2SiZr (Mr=748.28): Theoretical values: C, 72.23; H, 8.08; N, 3.74. Measured values: C, 72.21; H, 8.05; N, 3.76.

[0150] [Synthesis Example 13] (Preparation of Me(PhMeNCH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2Zr(NMe2)2(rac-MS-2a), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) Weigh out rac-MS-2 (1.49 g, 2 mmol) and dissolve it in Tol (100 mL) solvent. Add PhMeNCH=CH2 (0.293 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL used each time). Vacuum dry for 6 hours to obtain rac-MS-2a 1.62 g (92.2%), an orange solid.

[0151] The composition is C 54 H 71N3SiZr (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.

[0152] [Synthesis Example 14] (Preparation of Me(FcCH2CH2)Si(2-Me-7-p-tBuC6H4C9H4)2Zr(NMe2)2(rac-MS-2b), a silicon-crosslinked bisindenyl zirconocene compound containing ferrocenealkyl) The procedure is the same as in Synthesis Example 13, except that FcCH=CH2 (0.424 g, 2 mmol) is used instead of PhMeNCH=CH2 to obtain 1.4 g (87.7%) of meso-MS-1a, which is an orange-red solid. Of the FcCH=CH2, Fc=CpFe(C5H4) is the active component.

[0153] The composition is C 57 H 72 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.

[0154] [Preparation of precursors for synthesis examples 15 and 16] (Preparation of MeHSi(2-Me-7-PhC9H4)2ZrCl2(MS-3), a hydrogen-based silicon-crosslinked bisindenyl zirconocene compound) Weigh out 2-methyl-7-phenylindene (4.13 g, 20 mmol) and dissolve it in Tol (160 mL) of solvent. Slowly add n-butyllithium (2.4 M, 8.5 mL, 20 mmol) dropwise at -78°C, and allow to gradually return to room temperature and react overnight to obtain a wine-red solution. Slowly add methyldichlorosilane (1.04 mL, 10 mmol) dropwise at -78°C, allow to gradually return to room temperature and stir for more than 8 hours to obtain a yellow suspension. Place the yellow suspension at -78°C, slowly add n-butyllithium (2.4 M, 8.5 mL, 20 mmol) dropwise, allow to return to room temperature, and continue stirring for 2 hours to obtain an orange turbidity. Take zirconium tetrachloride (2.33 g, 10 mmol) in a glove box, place it in a vial, add 40 mL of toluene, remove the nitrogen protection, and add it to the above yellow suspension at room temperature. The color will immediately deepen from orange to brown-black, and allow to react for 1 day. The reaction mixture is filtered under the protection of nitrogen gas, the solvent is dried by suction from the resulting filtrate, and the mixture is washed with n-hexane, filtered, and dried by suction to obtain a yellow solid. The yellow solid is recrystallized in toluene at -20°C in a multi-step process to obtain rac-MS-3 1.25 g (18.7%), a racemic compound, and meso-MS-3 2.75 g (41.2%), a meso compound.

[0155] The composition is C 33 H 28 Cl2SiZr (Mr=614.79): Theoretical values: C, 64.47; H, 4.59. Measured values: C, 64.48; H, 4.61.

[0156] [Synthesis Example 15] (Preparation of Me(PhMeNCH2CH2)Si(2-Me-7-PhC9H4)2ZrCl2(rac-MS-3a), an amine alkyl-containing silicon-crosslinked bisindenyl zirconocene compound) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) solvent. Add PhMeNCH=CH2 (0.293 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL used each time). Vacuum dry for 6 hours to obtain rac-MS-3a 1.41 g (87.4%), an orange-red solid.

[0157] The composition is C 42 H 39 Cl2NSiZr(Mr=747.98): Theoretical values: C, 67.44; H, 5.26; N, 1.87. Measured values: C, 67.42; H, 5.27; N, 1.86.

[0158] [Synthesis Example 16] (Preparation of Me(FcCH2CH2)Si(2-Me-7-PhC9H4)2ZrCl2(rac-MS-3b), a silicon-crosslinked bisindenyl zirconocene compound containing ferrocenealkyl) The procedure is the same as in Synthesis Example 13, except that FcCH=CH2 (0.424 g, 2 mmol) is used instead of PhMeNCH=CH2, and finally, rac-MS-3b 1.53 g (86.7%), an orange-red solid, is obtained. Of the FcCH=CH2, Fc=CpFe(C5H4).

[0159] The composition is C 45 H 40 Cl2FeSiZr (Mr=826.86): Theoretical values: C, 65.37; H, 4.88. Measured values: C, 65.36; H, 4.89.

[0160] [Preparation of precursors for synthesis examples 16 and 17] (Production of MeHSiFlu2ZrCl2(MS-4), a hydrogen-silicon-bridged bisfluorenyl zirconocene compound) Weigh out fluorene (3.32 g, 20 mmol) and dissolve it in Tol (160 mL) of solvent. Slowly add n-butyllithium (2.4 M, 8.5 mL, 20 mmol) dropwise at -78°C, and allow to gradually return to room temperature and react overnight to obtain a wine-red solution. Slowly add methyldichlorosilane (1.04 mL, 10 mmol) dropwise at -78°C, allow to gradually return to room temperature and stir for more than 8 hours to obtain a yellow suspension. Place the yellow suspension at -78°C, slowly add n-butyllithium (2.4 M, 8.5 mL, 20 mmol) dropwise, allow to return to room temperature, and continue stirring for 2 hours to obtain an orange turbidity. Take zirconium tetrachloride (2.33 g, 10 mmol) in a glove box, place it in a vial, add 40 mL of toluene, remove the nitrogen protection, and add it to the above yellow suspension at room temperature. The color will immediately deepen from orange to brown, and allow to react for 1 day. The reaction mixture is filtered under the protection of nitrogen gas, the solvent is dried by suction from the resulting filtrate, and the mixture is washed with n-hexane, filtered, and dried by suction to obtain a yellow solid. The yellow solid is recrystallized with toluene at -20°C to obtain 3.89 g (72.8%) of compound MS-4.

[0161] The composition is C 27 H 20 Cl2SiZr (Mr=534.66): Theoretical values: C, 60.66; H, 3.77. Measured values: C, 60.64; H, 3.74.

[0162] [Synthesis Example 17] (Preparation of Me(PhMeNCH2CH2)SiFlu2ZrCl2(MS-4a), an amine alkyl-containing silicon-crosslinked bisfluorenyl zirconocene compound) Weigh out MS-4 (1.07 g, 2 mmol), dissolve it in Tol (100 mL) solvent, add PhMeNCH=CH2 (0.293 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount), and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL usage each time) of n-hexane. Vacuum dry for 6 hours to obtain 1.21 g (90.6%) of MS-4a, an orange solid.

[0163] The composition is C 36 H 31 Cl2NSiZr(Mr=667.85): Theoretical values: C, 64.74; H, 4.68; N, 2.10. Measured values: C, 64.73; H, 4.71; N, 2.11.

[0164] [Synthesis Example 18] (Preparation of Me(FcCH2CH2)SiFlu2ZrCl2(MS-4b), a silicon-crosslinked bisfluorenyl zirconocene compound containing ferrocenealkyl) The procedure is the same as in Synthesis Example 17, except that FcCH=CH2 (0.424 g, 2 mmol) is used instead of PhMeNCH=CH2, and finally, 1.32 g (88.4%) of MS-4b, an orange-red solid, is obtained. Of the FcCH=CH2, Fc=CpFe(C5H4).

[0165] The composition is C 39 H 32 Cl2FeSiZr (Mr=746.73): Theoretical values: C, 62.73; H, 4.32. Measured values: C, 62.72; H, 4.31.

[0166] [Synthesis Example 19] (Manufacturing of Me[(PhMeN(CH2)5)]Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) solvent. Add PhMeN(CH2)3CH=CH2 (0.388 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3c 1.49 g (86.2%), an orange-red solid.

[0167] The composition is C 45 H 45 Cl2NSiZr(Mr=790.97): Theoretical values: C, 68.41; H, 5.74; N, 1.77. Measured values: C, 68.44; H, 5.75; N, 1.76.

[0168] [Synthesis Example 20] (Manufacturing of Me[PhMeN(CH2)8]Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) solvent. Add PhMeN(CH2)6CH=CH2 (0.480 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3d 1.57 g (86.3%), an orange-red solid.

[0169] The composition is C 48 H 51 Cl2NSiZr(Mr=832.15): Theoretical values: C, 69.28; H, 6.18; N, 1.68. Measured values: C, 69.25; H, 6.16; N, 1.70.

[0170] [Synthesis Example 21] (Me[PhMeN(CH2) 12(Manufacturing of Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) solvent. Add PhMeN(CH2)9CH=CH2 (0.573 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3e 1.72 g (89.9%), an orange-red solid.

[0171] The composition is C 51 H 57 Cl2NSiZr(Mr=874.23): Theoretical values: C, 70.07; H, 6.57; N, 1.60. Measured values: C, 70.04; H, 6.55; N, 1.60.

[0172] [Synthesis Example 22] (Me[PhMeN(CH2) 15 (Manufacturing of Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol), dissolve it in Tol (100 mL) solvent, and prepare PhMeN(CH2) 12 CH=CH2 (0.666 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) are added, and the mixture is heated to 50°C and reacted for 24 hours. All volatile components are removed by vacuum at room temperature, and the remaining solid is washed 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL is used each time). After vacuum drying for 6 hours, rac-MS-3f 1.83 g (91.2%), an orange-red solid, is obtained.

[0173] The composition is C 54 H 63 Cl2NSiZr(Mr=916.31): Theoretical values: C, 70.78; H, 6.93; N, 1.53. Measured values: C, 70.76; H, 6.95; N, 1.52.

[0174] [Synthesis Example 23] (Manufacturing of Me[p-ClC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) of solvent. Add p-ClC6H4MeN(CH2)3CH=CH2 (0.461 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain 1.62 g (90.0%) of rac-MS-3 g, which is an orange-red solid.

[0175] The composition is C 45 H 44 Cl3NSiZr(Mr=824.51): Theoretical values: C, 65.55; H, 5.38; N, 1.70. Measured values: C, 65.56; H, 5.36; N, 1.72.

[0176] [Synthesis Example 24] (Manufacturing of Me[p-MeOC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) of solvent. Add p-MeOC6H4MeN(CH2)3CH=CH2 (0.454 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3h 1.60 g (89.2%), an orange-red solid.

[0177] The composition is C 46 H 46Cl2NOSiZr (Mr=819.09): Theoretical values: C, 67.45; H, 5.66; N, 1.71. Measured values: C, 67.47; H, 5.63; N, 1.72.

[0178] [Synthesis Example 25] (Manufacturing of Me[Fc(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) of solvent. Add 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 amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL is used each time). Vacuum dry for 6 hours to obtain rac-MS-3i 1.67 g (87.9%), an orange-red solid.

[0179] The composition is C 48 H 46 Cl2FeSiZr (Mr=868.95): Theoretical values: C, 66.35; H, 5.34. Measured values: C, 66.36; H, 5.33.

[0180] [Synthesis Example 26] (Manufacturing of Me(Fc(CH2)8)Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) of solvent. Add 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 amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL used each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3j 1.72 g (86.3%), an orange-red solid.

[0181] The composition is C51 H 52 Cl2FeSiZr (Mr=911.03): Theoretical values: C, 65.55; H, 5.38. Measured values: C, 65.56; H, 5.37.

[0182] [Synthesis Example 27] (Me[Fc(CH2) 12 (Manufacturing of Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol), dissolve it in Tol (100 mL) of solvent, and prepare 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, 5% usage amount) are added, and the mixture is heated to 50°C and reacted for 24 hours. All volatile components are removed by vacuum evacuation at room temperature, and the remaining solid is washed 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL is used each time). After vacuum drying for 6 hours, 1.98 g (93.6%) of rac-MS-3k, an orange-red solid, is obtained.

[0183] The composition is C 55 H 60 Cl2FeSiZr (Mr=967.14): Theoretical values: C, 68.31; H, 6.25. Measured values: C, 68.34; H, 6.27.

[0184] [Synthesis Example 28] (Me[Fc(CH2) 15 (Manufacturing of Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol), dissolve it in Tol (100 mL) of solvent, and prepare Fc(CH2) 13CH=CH2 (0.868 g, 2.2 mmol) (Note: Fc=CpFe(C5H4)) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) are added, and the mixture is heated to 50°C and reacted for 24 hours. All volatile components are removed by vacuum at room temperature, and the remaining solid is washed 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL is used each time). After vacuum drying for 6 hours, rac-MS-3l 2.02 g (91.5%), an orange-red solid, is obtained.

[0185] The composition is C 58 H 66 Cl2FeSiZr (Mr=1009.22): Theoretical values: C, 69.03; H, 6.59. Measured values: C, 69.04; H, 6.57.

[0186] [Synthesis Example 29] Refer to the cross-linking SiH group addition method, R 1 is a methyl group, R II Metallocene compounds in which the alkyl group is can be synthesized, and examples are shown below.

[0187] (Manufacturing of MenBuSi(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) of solvent. Add CH3CH2CH=CH2 (0.123 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3m 1.12 g (76.6%), an orange-red solid.

[0188] The composition is C 37 H 36 Cl2SiZr (Mr=670.90): Theoretical values: C, 66.24; H, 5.41. Measured values: C, 66.23; H, 5.40.

[0189] [Synthesis Example 30] (Manufacturing of Me[n-CH3(CH2)7]Si(2-Me-7-PhC9H4)2ZrCl2) Weigh out rac-MS-3 (1.34 g, 2 mmol) and dissolve it in Tol (100 mL) of solvent. Add CH3(CH2)5CH=CH2 (0.247 g, 2.2 mmol) and B(C6F5)3 (0.051 g, 0.1 mmol, 5% usage amount) and heat to 50°C and react for 24 hours. Remove all volatile components by vacuum at room temperature, and wash the remaining solid 2 to 4 times with small amounts (approximately 1.5 mL each time) of n-hexane. Vacuum dry for 6 hours to obtain rac-MS-3n 1.23 g (77.5%), an orange-red solid.

[0190] The composition is C 41 H 44 Cl2SiZr (Mr=727.01): Theoretical values: C, 67.74; H, 6.10. Measured values: C, 67.72; H, 6.11.

[0191] [Synthesis Example 31] Manufacturing of MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2 4-phenyl-2-methylindene (2.06 g, 10 mmol) is weighed out and dissolved in Tol (80 ml) solvent. At -78°C, n-butyllithium (2.4 M, 4.25 mL, 10 mmol) is slowly added dropwise, and the mixture is allowed to react overnight while gradually returning to room temperature to obtain a wine-red solution. At -78°C, methyldichlorosilane (1.04 mL, 10 mmol) is slowly added dropwise, and the mixture is stirred for at least 8 hours while gradually returning to room temperature to obtain a yellow suspension. The yellow suspension is left at -78°C, and t-butylaminelithium (0.79 g, 10 mmol) is slowly added dropwise. After returning to room temperature, the mixture is stirred for 2 hours to obtain an orange turbidity. The orange suspension is left at -78°C, and n-butyllithium (2.4 M, 8.5 mL, 20 mmol) is slowly added dropwise. After returning to room temperature, the mixture is stirred for 2 hours to obtain an orange turbidity. 2.33 g, 10 mmol of zirconium tetrachloride was taken from a glove box, placed in a vial, 40 mL of toluene was added, the nitrogen protection was removed, and the mixture was added to the orange suspension at room temperature. The color gradually deepened from orange to dark red, and the reaction was allowed to proceed for 1 day. The reaction mixture was filtered under nitrogen gas protection, the solvent was dried by suction from the resulting filtrate, and the mixture was washed with n-hexane, filtered, and dried by suction to obtain a red solid. The red solid was recrystallized in toluene at -20°C in a multi-step process to obtain the compound MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2 2.88 g (60.0%).

[0192] The composition is C 21 H 25 Cl2NSiZr(Mr=481.65): Theoretical values: C, 52.37; H, 5.23; N, 2.91. Measured values: C, 52.40; H, 5.21; N, 2.90.

[0193] [Synthesis Example 32] (Manufacturing of Me[Fc(CH2)5]Si(4-Ph-2-MeC9H4)(NtBu)ZrCl2) MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2 (0.96 g, 2 mmol) is weighed out and dissolved in 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, 5% used) are added, and the mixture is heated to 50°C and reacted for 24 hours. All volatile components are removed by vacuum at room temperature, and the remaining solid is washed 2 to 4 times with small amounts of n-hexane (approximately 1.5 mL used each time). After vacuum drying for 6 hours, 1.21 g (82.1%) of the dark red solid Me[Fc(CH2)5]Si(4-Ph-2-MeC9H4)(NtBu)ZrCl2 is obtained.

[0194] The composition is C 36 H 44 Cl2FeNSiZr (Mr=736.81): Theoretical values: C, 58.68; H, 6.02; N, 1.90. Measured values: C, 58.66; H, 6.03; N, 1.92.

[0195] (Production of B metallocene catalyst) [Manufacturing Example 1] 2 g of silica gel calcined at 600°C is weighed, 10 mL of 10% MAO-toluene solution (by weight) is added, and the mixture is heated to 80°C. A toluene solution of the metallocene compound shown in Formula 1 is added while stirring uniformly, controlling the Al / Zr ratio to 200:1, and the mixture is reacted overnight. The solid is collected by filtration, washed with toluene solvent until the washed solvent is colorless, and the solid is vacuum-dried for 24 hours to obtain a solid powder, which is stored in a glove box for use (unless otherwise specified below, this reaction procedure is used). Catalyst SC-1 with a specified metal content can be obtained by measuring the amount of charge and the metal content of the washed liquid, where the zirconium content is 0.268% (29.4 μmol / g).

[0196] [ka]

[0197] [Manufacturing Example 2] Two grams of silica gel, calcined at 600°C, are weighed out. Ten milliliters of a 10% MAO-toluene solution (by weight) and pure toluene are added. The mixture is heated to 80°C, stirred for 24 hours, filtered, and the solid is collected. The solid is washed three times with toluene and vacuum-dried for 24 hours to obtain solid powdered MAO-silica gel.

[0198] A certain amount of MAO-silica gel is weighed out, toluene is added to form a suspension, and a toluene solution of the metallocene zirconium compound is added while stirring uniformly, and the mixture is reacted overnight. The solid is collected by filtration, washed with toluene until the washed solvent is colorless, and the solid is vacuum-dried for 24 hours to obtain a solid powder, which is stored in a glove box for use. By measuring and calculating the zirconium content of the charge and the washed liquid, a catalyst with a specified zirconium content can be obtained.

[0199] A metallocene zirconium compound from Equation 1 is selected, and the Al / Zr ratio is controlled to 50:1, 100:1, and 150:1 to produce catalysts SC-2A (zirconium content of 0.846%, 100.2 μmol / g), SC-2B (zirconium content of 0.430%, 47.2 μmol / g), and SC-2C (zirconium content of 0.282%, 32.2 μmol / g), respectively.

[0200] [Manufacturing Example 3] The manufacturing steps are the same as in Manufacturing Example 2. A metallocene compound shown in Formula 2 is selected, and the Al / Zr ratio is controlled to 193:1, 227:1, and 340:1 to produce catalysts SC-3A (zirconium content of 0.40%, 28.4 μmol / g), SC-3B (zirconium content of 0.30%, 25.0 μmol / g), and SC-3C (zirconium content of 0.20%, 16.7 μmol / g), respectively.

[0201] [ka]

[0202] [Manufacturing Example 4] The manufacturing steps are the same as in Manufacturing Example 2. A metallocene compound shown in Formula 1 is selected, and the Al / Zr ratio is controlled to 193:1, 194:1, and 195:1 to produce catalysts SC-4A (zirconium content of 0.40%, 28.4 μmol / g), SC-4B (zirconium content of 0.40%, 28.5 μmol / g), and SC-4C (zirconium content of 0.40%, 28.7 μmol / g), respectively.

[0203] [Manufacturing Example 5] The manufacturing steps are the same as in Manufacturing Example 2. A metallocene compound shown in Equation 3 is selected, and the Al / Zr ratio is controlled to 50:1, 100:1, and 200:1 to produce catalysts SC-5A (zirconium content of 0.854%, 106.3 μmol / g), SC-5B (zirconium content of 0.441%, 49.2 μmol / g), and SC-5C (zirconium content of 0.277%, 30.8 μmol / g), respectively.

[0204] [ka]

[0205] [Manufacturing Example 6] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Equation 4 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-6 (zirconium content 0.453%, 51.2 μmol / g).

[0206] [ka]

[0207] [Manufacturing Example 7] The manufacturing steps are the same as in Manufacturing Example 2, and a metallocene compound shown in Equation 5 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-7 (zirconium content 0.441%, 48.7 μmol / g).

[0208] [ka]

[0209] [Manufacturing Example 8] The manufacturing steps are the same as in Manufacturing Example 2, and a metallocene compound shown in Equation 6 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-8 (zirconium content 0.437%, 50.7 μmol / g).

[0210] [ka]

[0211] [Manufacturing Example 9] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Equation 7 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-9 (zirconium content 0.463%, 52.4 μmol / g).

[0212] [ka]

[0213] [Manufacturing Example 10] The manufacturing steps are the same as in Manufacturing Example 2, and a metallocene compound shown in Equation 8 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-10 (zirconium content 0.425%, 47.1 μmol / g).

[0214] [ka]

[0215] [Manufacturing Example 11] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Equation 9 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-11 (zirconium content 0.439%, 48.3 μmol / g).

[0216] [ka]

[0217] [Manufacturing Example 12] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Equation 10 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-12 (zirconium content 0.482%, 52.1 μmol / g).

[0218] [ka]

[0219] [Manufacturing Example 13] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Formula 11 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-13 (zirconium content 0.501%, 54.3 μmol / g).

[0220] [ka]

[0221] [Manufacturing Example 14] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Formula 12 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-14 (zirconium content 0.410%, 44.6 μmol / g).

[0222] [ka]

[0223] [Manufacturing Example 15] 2.0 g of silica gel calcined at 600°C is weighed out, 10 mL of 10% MAO-toluene solution (by weight) is added, then 0.30 g of dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate is added, followed by 10 mL of toluene. The mixture is heated to 80°C, stirred for 24 hours, filtered, and the solid is collected. The solid is washed three times with toluene solvent and vacuum-dried for 24 hours to obtain 3.1 g of solid powdered carrier silica gel.

[0224] 2 g of treated silica gel is weighed out, 20 mL of toluene solvent is added to form a suspension, and 5 mL of toluene solution prepared with 100 mg of the metallocene zirconium compound shown in formula 12 is added while stirring uniformly, and the mixture is stirred overnight at room temperature. The solid is collected by filtration, washed with toluene solvent until the washed solvent is colorless, and the solid is 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 is stored in a glove box for use.

[0225] [Manufacturing Example 16] The only difference from Production Example 15 is that the same mass of tris(pentafluorophenyl)borane is used instead of dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, and no other conditions are changed. 3.2 g of solid catalyst is obtained, and the measured zirconium content of the catalyst is 0.45% by mass.

[0226] [Manufacturing Example 17] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Formula 13 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-16 (zirconium content 0.406%, 43.7 μmol / g).

[0227] [ka]

[0228] [Manufacturing Example 18] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Formula 14 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-17 (zirconium content 0.415%, 45.9 μmol / g).

[0229] [ka]

[0230] [Manufacturing Example 19] The manufacturing steps are the same as in Manufacturing Example 2, a metallocene compound shown in Equation 15 is selected, and the Al / Zr ratio is controlled to 100:1 to produce catalyst SC-18 (zirconium content 0.371%, 40.2 μmol / g).

[0231] [ka]

[0232] [Manufacturing Example 20] Some metallocene compounds from Synthesis Examples 2-18 were selected and used to produce catalysts for olefin polymerization reactions. The manufacturing process is as follows:

[0233] Two grams of silica gel, calcined at 600°C, are weighed out. Ten milliliters of a 10% MAO-toluene solution (by weight) and 40-100 milliliters of pure toluene solvent are added. The mixture is heated to 80°C, stirred for 24 hours, filtered, and the solid is collected. The solid is washed three times with toluene solvent and vacuum-dried for 24 hours to obtain solid powdered MAO-silica gel.

[0234] A certain amount of MAO-silica gel is weighed out, toluene solvent is added to form a suspension, and toluene solutions of some of the zirconocene compounds from the examples are added while stirring uniformly, and the mixture is reacted overnight. The solid is collected by filtration, washed with toluene solvent until the washed-out solvent is colorless, and the solid is vacuum-dried for 24 hours to obtain a solid powder, which is stored in a glove box for use. By measuring and calculating the zirconium content of the charge and the washed-out liquid, a catalyst with a specified zirconium content can be obtained.

[0235] Here, The Al / Zr ratio was controlled to 200:1, and the zirconocene compound rac-MS-1b was selected to produce the catalyst rac-MS-1b-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0236] The Al / Zr ratio was controlled to 50:1, and the zirconocene compound rac-MS-1j was selected to produce the catalyst rac-MS-1j-C, which has a zirconium content of 0.846% (100.2 μmol / g).

[0237] The Al / Zr ratio was controlled to 100:1, and the zirconocene compound rac-MS-3a was selected to produce the catalyst rac-MS-3a-C, which has a zirconium content of 0.430% (47.2 μmol / g).

[0238] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound rac-MS-3b was selected to produce the catalyst rac-MS-3b-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0239] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound rac-MS-4a was selected to produce the catalyst rac-MS-4a-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0240] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound rac-MS-4b was selected to produce the catalyst rac-MS-4b-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0241] [Manufacturing Example 21] The metallocene compounds produced in Synthesis Examples 19-32 were selected and used to produce catalysts for olefin polymerization reactions. The production process is as follows:

[0242] Two grams of silica gel, calcined at 600°C, are weighed out. Ten milliliters of a 10% MAO-toluene solution (by weight) and 40-100 milliliters of pure toluene solvent are added. The mixture is heated to 80°C, stirred for 24 hours, filtered, and the solid is collected. The solid is washed three times with toluene solvent and vacuum-dried for 24 hours to obtain solid powdered MAO-silica gel.

[0243] A certain amount of MAO-silica gel is weighed out, toluene solvent is added to form a suspension, and toluene solutions of some of the zirconocene compounds from the examples are added while stirring uniformly, and the mixture is reacted overnight. The solid is collected by filtration, washed with toluene solvent until the washed-out solvent is colorless, and the solid is vacuum-dried for 24 hours to obtain a solid powder, which is stored in a glove box for use. By measuring and calculating the zirconium content of the charge and the washed-out liquid, a catalyst with a specified zirconium content can be obtained.

[0244] Here, The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[(PhMeN(CH2)5)]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3c-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0245] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[PhMeN(CH2)8]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3d-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0246] The Al / Zr ratio is controlled to 200:1, and the zirconocene compound Me[PhMeN(CH2)] 12 ]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to prepare the catalyst rac-MS-3e-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0247] The Al / Zr ratio is controlled to 200:1, and the zirconocene compound Me[PhMeN(CH2)] 15]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to prepare the catalyst rac-MS-3f-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0248] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[p-ClC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3g-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0249] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[p-MeOC6H4MeN(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3h-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0250] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[Fc(CH2)5]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3i, which has a zirconium content of 0.268% (29.4 μmol / g).

[0251] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me(Fc(CH2)8)Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3j, which has a zirconium content of 0.268% (29.4 μmol / g).

[0252] The Al / Zr ratio is controlled to 200:1, and the zirconocene compound Me[Fc(CH2)] 12 ]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to prepare the catalyst rac-MS-3k-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0253] The Al / Zr ratio is controlled to 200:1, and the zirconocene compound Me[Fc(CH2)] 15]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to prepare catalyst rac-MS-3l, where the zirconium content was 0.268% (29.4 μmol / g).

[0254] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound MenBuSi(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3m-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0255] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[n-CH3(CH2)7]Si(2-Me-7-PhC9H4)2ZrCl2 was selected to produce the catalyst rac-MS-3n-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0256] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound MeHSi(4-Ph-2-MeC9H4)(NtBu)ZrCl2 was selected to produce the catalyst rac-MS-3o-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0257] The Al / Zr ratio was controlled to 200:1, and the zirconocene compound Me[Fc(CH2)5]Si(4-Ph-2-MeC9H4)(NtBu)ZrCl2 was selected to produce the catalyst rac-MS-3p-C, which has a zirconium content of 0.268% (29.4 μmol / g).

[0258] C-catalyzed reaction [Example 1] A 300 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0259] The belt pressurized catalyst device is dried and transferred to a glove box. A predetermined amount of catalyst is added, along with a small amount of solvent, and mixed uniformly. After removing it from the glove box and attaching it to the high-pressure reactor, polymerization experiments can be performed.

[0260] The polymerization experimental conditions are as follows: a constant temperature, pressure, and reaction time are set. Considering application to industrial production, the polymerization experiments already completed will prioritize the selection of co-catalysts, i.e., avoiding or minimizing the use of expensive MAO and switching to inexpensive alkylaluminum reagents. (Unless otherwise specified below, this reaction procedure will be used).

[0261] Select 200 mg of SC-1 catalyst, use no solvent, react for 30 minutes, react at 80°C, and inject 50 g of propylene under pressure.

[0262] 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 That is the case.

[0263] [Example 2] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0264] 105 mg of SC-2A catalyst and 8 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 500:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0265] Finally, 92g of polymer was obtained, and the calculated polymerization activity was 4.00 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 131324, the Mw value was 325745, and the PDI value was 2.48. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.4%. The melting point is 151.33°C. (Note: PP analysis is selective.) [Example 3] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0266] 105 mg of SC-2B catalyst and 3.2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 200:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0267] Finally, 64 g of polymer was obtained, and the calculated polymerization activity was 2.78 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0268] [Example 4] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0269] 106 mg of SC-2C catalyst and 3.2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 200:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0270] Finally, 57 g of polymer was obtained, and the calculated polymerization activity was 2.45 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0271] [Example 5] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0272] 105 mg of SC-3A catalyst and 8 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 500:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0273] Finally, 80g of polymer was obtained, and the calculated polymerization activity was 3.48 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 133064, the Mw value was 313745, and the PDI value was 2.36. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.3%. The melting point is 149.43°C.

[0274] [Example 6] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0275] 105 mg of SC-3B catalyst and 3.2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 200:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0276] Finally, 52 g of polymer was obtained, and the calculated polymerization activity was 2.26 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0277] [Example 7] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0278] 106 mg of SC-3C catalyst, 3.2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum zirconium ratio of about 200:1), a reaction time of 180 minutes, a reaction temperature of 75 °C, and a propylene pressure > 3.9 MPa.

[0279] Finally, 43 g of polymer was obtained, and the calculated polymerization activity was 1.85×10 7 g(PP)·mol -1 (Zr)·h -1 is.

[0280] [Example 8] A 2000 mL high-pressure reactor was selected, evacuated under vacuum in an oil bath at 100 °C, and replaced with nitrogen gas three times before being prepared for use. [[ID=tmp17]] [[ID=tmp18]]

[0281] [[ID=tmp19]] 98 mg of SC-4A catalyst, 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum zirconium ratio of about 549:1), a reaction time of 240 minutes, a reaction temperature of 75 °C, and a propylene amount of 528.7 g.

[0282] [[ID=tmp24]]Finally, 450 g of polymer was obtained, and the calculated polymerization activity was 1.098×10 8 g(PP)·mol -1 (Zr)·h -1 is. The Mn measured by high-temperature GPC was 162913, the Mw was 377577, and the PDI value was 2.317. High-temperature 13 The isotacticity measured by 13C NMR spectrum was [mmmm] 99.6%. The melting point test value was 151.4 °C.

[0283] [Example 9] A 2000 mL high-pressure reactor was selected, evacuated under vacuum in an oil bath at 100 °C, and replaced with nitrogen gas three times before being prepared for use.

[0284] 60 mg of SC-4A catalyst, 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-to-zirconium ratio of about 896:1), a reaction time of 330 minutes, a reaction temperature of 75 °C, and a propylene amount of 518 g were selected.

[0285] Finally, 860 g of polymer was obtained, and the calculated polymerization activity was 1.772×10 8 g(PP)·mol -1 (Zr)·h -1 . The Mn measured by high-temperature GPC was 104205, the Mw was 226218, and the PDI value was 2.17. The high-temperature 13 isotacticity measured by 13C NMR spectrum was [mmmm] 98.4%. The melting point test value was 152.2 / 161.4 °C.

[0286] [Example 10] A 2000 mL high-pressure reactor was selected, evacuated under vacuum in a 100 °C oil bath, and replaced three times with nitrogen gas before being prepared for use.

[0287] 60 mg of SC-4A catalyst, 3 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-to-zirconium ratio of about 1195:1), a reaction time of 180 minutes, a reaction temperature of 75 °C, a propylene amount of 538 g, and a hydrogen gas amount of 0.02 g were selected. <​​​​​​​​​​​​​​​​​​35 mg of SC-4A catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1707:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0291] 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 That is the case.

[0292] [Example 12] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0293] 65 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1792:1) were selected. The reaction time was 270 minutes, the reaction temperature was 75°C, the amount of propylene was 659 g, and the amount of hydrogen gas was 0.026 g.

[0294] Finally, 600g of polymer was obtained, and the calculated polymerization activity was 2.206 × 10⁻⁶ 8 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 80551, the Mw value was 188015, and the PDI value was 2.33. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.7%. The melting point is 151.83 / 152.2°C.

[0295] [Example 13] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0296] 40 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1707:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 628.6 g, and the amount of hydrogen gas was 1.365 g.

[0297] Finally, 270g of polymer was obtained, and the calculated polymerization activity was 1.613 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0298] [Example 14] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0299] 30 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 2389:1) were selected. The reaction time was 360 minutes, the reaction temperature was 75°C, the amount of propylene was 658.8 g, and the amount of hydrogen gas was 0.052 g.

[0300] 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 The Mn value measured by high-temperature GPC was 47736, the Mw value was 146937, and the PDI value was 3.08.

[0301] [Example 15] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0302] 30 mg of SC-4A catalyst and 20 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 2389:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 357.2 g, and the amount of hydrogen gas was 0.06 g.

[0303] 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 The melting point test value is 154.03°C.

[0304] [Example 16] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0305] 30 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1195:1) were selected. The reaction time was 420 minutes, the reaction temperature was 75°C, the amount of propylene was 682 g, and the amount of hydrogen gas was 0.06 g.

[0306] Finally, 540g of polymer was obtained, and the calculated polymerization activity was 4.301 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0307] [Example 17] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0308] 20 mg of SC-4A catalyst and 3.5 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 627:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 657 g, and the amount of hydrogen gas was 0.06 g.

[0309] 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 That is the case.

[0310] [Example 18] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0311] 20 mg of SC-4A catalyst and 7 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1254:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 651 g, and the amount of hydrogen gas was 0.06 g.

[0312] 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 That is the case.

[0313] [Example 19] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0314] 20 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1792:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 654 g, and the amount of hydrogen gas was 0.06 g.

[0315] 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 That is the case.

[0316] [Example 20] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0317] 20 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1792:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 652 g, and the amount of hydrogen gas was 0.06 g.

[0318] 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 That is the case.

[0319] [Example 21] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0320] 30 mg of SC-4A catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1195:1) were selected. The reaction time was 420 minutes, the reaction temperature was 75°C, the amount of propylene was 670 g, and the amount of hydrogen gas was 0.06 g.

[0321] Finally, 530g of polymer was obtained, and the calculated polymerization activity was 4.221 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0322] [Example 22] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0323] 30 mg of SC-4B catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1195:1) were selected. The reaction time was 480 minutes, the reaction temperature was 75°C, the amount of propylene was 684 g, and the amount of hydrogen gas was 0.06 g.

[0324] 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 That is the case.

[0325] [Example 23] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then purged three times with nitrogen gas before being prepared for use. 30 mg of SC-4B catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1195:1) were selected. The reaction time was 240 minutes, the reaction temperature was 75°C, the amount of propylene was 687.5 g, and the amount of hydrogen gas was 0.06 g.

[0326] Finally, 533g of polymer was obtained, and the calculated polymerization activity was 4.245 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 The melting point test value is 155.46°C.

[0327] [Example 24] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0328] 30 mg of SC-4B catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1195:1) were selected. The reaction time was 240 minutes, the reaction temperature was 75°C, the amount of propylene was 688.6 g, and the amount of hydrogen gas was 0.06 g.

[0329] Finally, 405 g of polymer was obtained, and the calculated polymerization activity was 3.226 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0330] [Example 25] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0331] 30 mg of SC-4C catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1195:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 680 g, and the amount of hydrogen gas was 0.06 g.

[0332] Finally, 530g of polymer was obtained, and the calculated polymerization activity was 4.221 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0333] [Example 26] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0334] 20 mg of SC-4C catalyst and 10 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 1792:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 681 g, and the amount of hydrogen gas was 0.06 g.

[0335] 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 That is the case.

[0336] [Example 27] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0337] 98 mg of SC-5A catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were selected. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 523 g.

[0338] Finally, 461 g of polymer was obtained, and the calculated polymerization activity was 1.106 × 10⁶ 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 174912, the Mw value was 366583, and the PDI value was 2.09. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]98.4%. The melting point is 153.1°C.

[0339] [Example 28] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0340] A 60 mg SC-5B catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 896:1) were selected. The reaction time was 330 minutes, the reaction temperature was 75°C, and the amount of propylene was 521 g.

[0341] 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 The Mn value measured by high-temperature GPC was 115708, the Mw value was 236654, and the PDI value was 2.045. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.1%. The melting point is 154.9°C.

[0342] [Example 29] A 2000 mL high-pressure reactor was selected, evacuated under vacuum in an oil bath at 100 °C, and replaced with nitrogen gas three times before use.

[0343] 60 mg of SC-5C catalyst and 3 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum zirconium ratio of about 1195:1) were selected. The reaction time was 180 minutes, the reaction temperature was 75 °C, the amount of propylene was 534 g, and the amount of hydrogen gas was 0.02 g.

[0344] Finally, 91 g of polymer was obtained, and the calculated polymerization activity was 1.641×10 7 g(PP)·mol -1 (Zr)·h -1 is.

[0345] [Example 30] A 2000 mL high-pressure reactor was selected, evacuated under vacuum in an oil bath at 100 °C, and replaced with nitrogen gas three times before use.

[0346] 98 mg of SC-6 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum zirconium ratio of about 549:1) were weighed. The reaction time was 240 minutes, the reaction temperature was 75 °C, and the amount of propylene was 541 g.

[0347] Finally, 424 g of polymer was obtained, and the calculated polymerization activity was 2.112×10 7 g(PP)·mol -1 (Zr)·h -1 is. The Mn measured by high-temperature GPC was 168742, the Mw was 368213, and the PDI value was 2.18. High temperature 13 The isotacticity measured by 13C NMR spectrum was [mmmm] 98.9%. The melting point test value was 155.4 °C.

[0348] [Example 31] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0349] 100 mg of SC-7 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 539 g.

[0350] Finally, 447g of polymer was obtained, and the calculated polymerization activity was 2.294 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 198563, the Mw value was 398423, and the PDI value was 2.01. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.2%. The melting point is 157.1°C.

[0351] [Example 32] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0352] 100 mg of SC-8 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 534 g.

[0353] Finally, 451 g of polymer was obtained, and the calculated polymerization activity was 2.223 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn measured by high-temperature GPC was 215821, Mw was 439429, and the PDI value was 2.036. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.4%. The melting point is 159.1°C.

[0354] [Example 33] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0355] 100 mg of SC-9 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 544 g.

[0356] Finally, 472g of polymer was obtained, and the calculated polymerization activity was 2.252 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 175941, the Mw value was 419745, and the PDI value was 2.386. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.5%. The melting point is 161.4°C.

[0357] [Example 34] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0358] 100 mg of SC-10 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 521 g.

[0359] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 2.489 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 155967, the Mw value was 430741, and the PDI value was 2.762. 13The isotacticity measured by 13C NMR spectroscopy is [mmmm]97.2%. The melting point is 147.9°C.

[0360] [Example 35] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0361] 100 mg of SC-11 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 521 g.

[0362] 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 The Mn measured by high-temperature GPC was 152134, the Mw was 416572, and the PDI value was 2.738. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]97.5%. The melting point is 148.1°C.

[0363] [Example 36] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0364] 100 mg of SC-12 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 529 g.

[0365] Finally, 487g of polymer was obtained, and the calculated polymerization activity was 2.336 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1The Mn value measured by high-temperature GPC was 142879, the Mw value was 396654, and the PDI value was 2.776. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]96.6%. The melting point is 144.7°C.

[0366] [Example 37] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0367] 100 mg of SC-13 catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 542 g.

[0368] 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 The Mn value measured by high-temperature GPC was 162678, the Mw value was 396789, and the PDI value was 2.439. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]97.6%. The melting point is 152.9°C.

[0369] [Example 38] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0370] 100 mg of SC-14 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were weighed out, the reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 582 g.

[0371] 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 The Mn value measured by high-temperature GPC was 182668, the Mw value was 406769, and the PDI value was 2.226. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]95.6%. The melting point is 147.9°C.

[0372] [Example 39] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0373] 100 mg of SC-15 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were weighed out, the reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 552 g.

[0374] Finally, 485g of polymer is obtained. The PDI value measured by high-temperature GPC is 2.028. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]96.3%. The melting point is 148.5°C.

[0375] [Example 40] The evaluation conditions are the same as in Example 39, and the catalyst produced in Production Example 16 is used. 560g of propylene is used, and 300g of polypropylene powder is obtained. The PDI in the GPC test is 2.678, and at high temperature 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]92.6%. The melting point is 145.1°C.

[0376] [Example 41] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0377] 100 mg of SC-16 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were weighed out, the reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 582 g.

[0378] Finally, 418 g of polymer was obtained, and the calculated polymerization activity was 2.434 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 172761, the Mw value was 435432, and the PDI value was 2.520. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]96.7%. The melting point is 148.8°C.

[0379] [Example 42] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0380] 100 mg of SC-17 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were weighed out, the reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 582 g.

[0381] 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 The Mn value measured by high-temperature GPC was 123758, the Mw value was 467327, and the PDI value was 3.776. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]92.4%. The melting point is 140.2°C.

[0382] [Example 43] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0383] 100 mg of SC-18 catalyst and 15 mL of triisobutylaluminum (concentration 150 μmol / mL) were weighed out, the reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 582 g.

[0384] 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 The Mn value measured by high-temperature GPC was 186469, the Mw value was 404219, and the PDI value was 2.168. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]97.2%. The melting point is 148.7°C.

[0385] [Example 44] For the polymerization reaction, a 300 mL high-pressure reaction vessel (unless otherwise specified, a 300 mL reaction vessel will be used in all subsequent cases) is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0386] The belt pressurized catalyst device is dried and transferred to a glove box. A predetermined amount of catalyst is added, along with a small amount of solvent, and mixed uniformly. After removing it from the glove box and attaching it to the high-pressure reactor, polymerization experiments can be performed.

[0387] The polymerization experimental conditions are as follows: a constant temperature, pressure, and reaction time are set. Considering application to industrial production, the polymerization experiments already completed will prioritize the selection of co-catalysts, that is, they will be replaced with inexpensive alkylaluminum reagents, either by not using expensive MAO or by using it in minimal amounts.

[0388] Weigh out 50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum / zirconium ratio of approximately 200), set the reaction time to 60 minutes, the reaction temperature to 50°C, and the ethylene pressure in the vessel to 1 MPa.

[0389] Finally, 10 g of polymer was obtained, and the calculated polymerization activity was 6.8 × 10⁻⁶. 6 g(PE)·mol -1 (Zr)·h -1 That is the case.

[0390] [Example 45] The polymerization conditions were basically the same as in Example 44, with the differences being as follows: 50 mg of rac-MS-1b-C catalyst and 2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum / zirconium ratio of approximately 200) were weighed out, the reaction time was set to 60 minutes, the reaction temperature to 50°C, and the ethylene pressure to 2 MPa.

[0391] 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 That is the case.

[0392] [Example 46] The polymerization conditions were basically the same as in Example 44, with the differences being as follows: 150 mg of rac-MS-1b-C catalyst and 0.2 mL of MAO (specifications 10% mass in Tol, aluminum / zirconium ratio approximately 200:1) were weighed out, the reaction time was set to 60 minutes, the reaction temperature to 50°C, and the ethylene pressure to 1 MPa.

[0393] Finally, 35 g of polymer was obtained, and the calculated polymerization activity was 6.99 × 10⁻⁶. 6 g(PE)·mol -1 (Zr)·h -1 That is the case.

[0394] [Example 47] The polymerization conditions were basically the same as in Example 44, with the differences being as follows: 113 mg of rac-MS-1j-C catalyst and 15 mL of triisobutylaluminum solution (with a concentration of 150 μmol / mL and an aluminum / zirconium ratio of approximately 200:1) were weighed out, the reaction time was set to 60 minutes, the reaction temperature to 50°C, and the ethylene pressure to 1 MPa.

[0395] 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 That is the case.

[0396] [Example 48] The polymerization conditions were basically the same as in Example 44, with the following differences: 150 mg of rac-MS-3a-C catalyst and 6.3 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum / zirconium ratio of approximately 200:1) were weighed out, the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 1 MPa.

[0397] Finally, 21 g of polymer was obtained, and the calculated polymerization activity was 4.45 × 10⁻⁶. 6 g(PE)·mol -1 (Zr)·h -1 That is the case.

[0398] [Example 49] The polymerization conditions were basically the same as in Example 44, with the differences being as follows: 150 mg of rac-MS-3b-C catalyst and 1.75 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 200:1) were weighed out, the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 1 MPa.

[0399] Finally, 36 g of polymer was obtained, and the calculated polymerization activity was 2.74 × 10⁻⁶. 7 g(PE)·mol -1 (Zr)·h-1 That is the case.

[0400] [Example 50] The polymerization conditions were basically the same as in Example 44, with the following differences: 150 mg of rac-MS-4a-C catalyst and 6.3 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum / zirconium ratio of approximately 200:1) were weighed out, the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 1 MPa.

[0401] Finally, 54 g of polymer was obtained, and the calculated polymerization activity was 1.22 × 10⁻⁶ 7 g(PE)·mol -1 (Zr)·h -1 That is the case.

[0402] [Example 51] The polymerization conditions were basically the same as in Example 44, with the differences being as follows: 150 mg of rac-MS-4b-C catalyst and 3.75 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 200:1) were weighed out, the reaction time was 60 minutes, the reaction temperature was 50°C, and the ethylene pressure was 2 MPa.

[0403] 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 That is the case.

[0404] [Example 52] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0405] 112 mg of rac-MS-1b-C catalyst and 8 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 500:1) were weighed out, the reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0406] Finally, 91 g of polymer was obtained, and the calculated polymerization activity was 9.20 × 10⁻⁶. 6 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 133945, the Mw value was 342375, and the PDI value was 2.57. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.3%. The melting point is 157.63°C.

[0407] [Example 53] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0408] 101 mg of rac-MS-1j-C catalyst and 3.2 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, and the propylene pressure was >3.9 MPa.

[0409] 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 The Mn value measured by high-temperature GPC was 127361, the Mw value was 36.431, and the PDI value was 2.83. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]98.6%. The melting point is 152.3°C.

[0410] [Example 54] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0411] 104 mg of rac-MS-1b-C catalyst and 15 mL of triisobutylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, and the amount of propylene was 528.7 g.

[0412] Finally, 412 g of polymer was obtained, and the calculated polymerization activity was 3.37 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 173453, the Mw value was 394257, and the PDI value was 2.273. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]99.1%. The melting point is 154.4°C.

[0413] [Example 55] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0414] 104 mg of rac-MS-1b-C catalyst and 15 mL of triethylaluminum (with a concentration of 150 μmol / mL and an aluminum-zirconium ratio of approximately 549:1) were weighed out. The reaction time was 240 minutes, the reaction temperature was 75°C, the amount of propylene was 538 g, and the amount of hydrogen gas was 0.02 g.

[0415] Finally, 478g of polymer was obtained, and the calculated polymerization activity was 1.54 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 135427, the Mw value was 397892, and the PDI value was 2.938. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]98.4%. The melting point is 153.2°C.

[0416] [Example 56] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0417] 35 mg of rac-MS-1j-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1707:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0418] Finally, 135 g of polymer was obtained, and the calculated polymerization activity was 4.37 × 10⁻⁶. 7 g(PP)·mol -1 (Zr)·h -1 The Mn value measured by high-temperature GPC was 82451, the Mw value was 213509, and the PDI value was 2.59. 13 The isotacticity measured by 13C NMR spectroscopy is [mmmm]96.7%. The melting point is 147.83 / 150.2°C.

[0419] [Example 57] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0420] 35 mg of rac-MS-3c-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0421] Finally, 469 g of polymer was obtained, and the calculated polymerization activity was 1.52 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0422] [Example 58] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0423] 35 mg of rac-MS-3d-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0424] Finally, 455 g of polymer was obtained, and the calculated polymerization activity was 1.47 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0425] [Example 59] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0426] 35 mg of rac-MS-3e-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0427] Finally, 492g of polymer was obtained, and the calculated polymerization activity was 1.59 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0428] [Example 60] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0429] 35 mg of rac-MS-3f-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0430] 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 That is the case.

[0431] [Example 61] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0432] 35 mg of rac-MS-3g-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0433] Finally, 387g of polymer was obtained, and the calculated polymerization activity was 1.25 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0434] [Example 62] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0435] 35 mg of rac-MS-3h-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0436] Finally, 418 g of polymer was obtained, and the calculated polymerization activity was 1.35 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0437] [Example 63] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0438] 35 mg of rac-MS-3i-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0439] 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 That is the case.

[0440] [Example 64] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0441] 35 mg of rac-MS-3j-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0442] Finally, 427g of polymer was obtained, and the calculated polymerization activity was 1.38 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0443] [Example 65] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0444] 35 mg of rac-MS-3k-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0445] Finally, 434 g of polymer was obtained, and the calculated polymerization activity was 1.41 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0446] [Example 66] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0447] 35 mg of rac-MS-3l-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0448] Finally, 395g of polymer was obtained, and the calculated polymerization activity was 1.27 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0449] [Example 67] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0450] 35 mg of rac-MS-3p-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0451] 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 That is the case.

[0452] [Comparative Example 1] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0453] 35 mg of rac-MS-3m-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0454] Finally, 425g of polymer was obtained, and the calculated polymerization activity was 1.38 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0455] [Comparative Example 2] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0456] 35 mg of rac-MS-3n-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0457] Finally, 420g of polymer was obtained, and the calculated polymerization activity was 1.36 × 10⁻⁶. 8 g(PP)·mol -1 (Zr)·h -1 That is the case.

[0458] [Comparative Example 3] A 2000 mL high-pressure reaction vessel is selected, evacuated using a 100°C oil bath, and then prepared for use after being replaced three times with nitrogen gas.

[0459] 35 mg of rac-MS-3o-C catalyst and 2.5 mL of triethylaluminum (with a concentration of 100 μmol / mL and an aluminum-zirconium ratio of approximately 1200:1) were weighed out. The reaction time was 180 minutes, the reaction temperature was 75°C, the amount of propylene was 512 g, and the amount of hydrogen gas was 0.02 g.

[0460] 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 That is the case.

[0461] To facilitate comparison and analysis, the above experimental data is summarized in the table below.

[0462] [Table 1]

[0463] [Table 2]

[0464] [Table 3]

[0465] The following can be seen from the data in Tables 1-3.

[0466] 1) When the substituents on the crosslinking atoms in the talocene compound include C2-C4 groups substituted with amine groups or C1-C3 groups substituted with metallocene groups, the prepared catalyst has high catalytic activity for the polymerization of propylene, and a polymerization product with appropriate molecular weight, PDI value, isotacticity, and melting point can be obtained.

[0467] 2) By adjusting the type of substituents on the crosslinking atoms in the metallocene compound, polymerization products with different molecular weights and melting points can be obtained.

[0468] 3) By adjusting test conditions such as the Al / Zr ratio of the catalyst and / or the Al / Zr ratio of the polymerization system, the polymerization activity of the catalyst can be further optimized. For example, this point was explained in Examples 1-4 and 8-21.

[0469] [Table 4]

[0470] The following can be seen from the data in Table 4.

[0471] 1) When the substituent on the bridging atom in the metallocene compound contains a C2 group substituted with an amine or a C2 group substituted with a metallocene group, the produced catalyst has high catalytic activity for the polymerization of ethylene.

[0472] 2) By adjusting test conditions such as the Al / Zr ratio of the catalyst and / or the Al / Zr ratio of the polymerization system, the polymerization activity of the catalyst can be further optimized, as illustrated in Examples 44-45.

[0473] [Table 5]

[0474] The following can be seen from the data in Table 5.

[0475] 1) When the substituent on the bridging atom in the metallocene compound contains a C2 group substituted with an amine group or a C2 group substituted with a metallocene group, the produced catalyst has high catalytic activity for the polymerization of propylene.

[0476] 2) 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, as illustrated in Examples 52, 54, and 55.

[0477] [Table 6]

[0478] The following can be seen from the data in Table 6.

[0479] C5-C5 15 C5-C substituted with a group or metallocene group 15 When it is a compound, the manufactured catalyst has high catalytic activity for the polymerization of propylene.

[0480] The following can be seen from the data in Tables 1-6.

[0481] Compared to metallocene compounds where the substituents on the crosslinking atoms are not amine-substituted or metallocene-substituted, the catalyst produced when the substituents on the crosslinking atoms in the metallocene compound are amine-substituted or metallocene-substituted has higher catalytic activity for the polymerization of propylene.

Claims

1. It is a metallocene compound, and its structure is as shown in formula (I), 【Chemistry 1】 In equation (I), R Ｉ and R ＩＩ They are the same or different, and R Ｉ and R ＩＩ At least one of them is a C substituted with an amine group. １ ~C ６ C substituted with hydrocarbon groups and amine groups １ ~C ６ Selected from halogenated hydrocarbon groups, R Ｉ and R ＩＩ If only one of the groups of R and R is selected from the groups defined above, the other group is a C １ to C ６ hydrocarbon group selected from, Z is selected from silicon, Cp ＩＩＩ R is a substituted cyclopentadienyl group, a substituted indenyl group, or a substituted fluorenyl group, as shown in formula (II). ｉ , R ｉｉ , R ｉｉｉ These are the substituents on the corresponding ring, 【Chemistry 2】 In equation (II), R ｉ is hydrogen, C １ ~C １０ Selected from hydrocarbon groups, R ｉｉ and R ｉｉｉ They are either the same or different, and each independently contains hydrogen and C ６ ~C １０ Aryl group, and C ７ ~C ２０ Selected from alkylaryl groups, and R ｉ , R ｉｉ and R ｉｉｉ It is not hydrogen at the same time, E is NR ｉｖ or PR ｉｖ And, R ｉｖ C contains hydrogen and straight or branched chains, saturated or unsaturated, heteroatoms, or does not contain heteroatoms. １ ~C ２０ Selected from hydrocarbon groups, M is selected from Zr, L ＩＶ and L Ｖ They are the same or different, and each independently contains hydrogen, chlorine, a dimethylamine group, and C, which is linear or branched, saturated or unsaturated, contains a heteroatom or does not contain a heteroatom. １ ~C ２０ Selected from hydrocarbons, n is 2, The amine group is as shown in formula (III), 【Transformation 3】 In equation (III), R ａ and R ｂ They are the same or different, and each is independent of C １ ~C ６ alkyl group, C ６ ~C １２ Aryl group, and C ７ ~C １０ A metallocene compound selected from arylalkyl groups.

2. In equation (III), R ａ and R ｂ They are the same or different, and each is independently C １ ~C ４ Alkyl groups, phenyl groups and C ７ ~C ９ The metallocene compound according to claim 1, characterized by being selected from arylalkyl groups.

3. In equation (I), L ＩＶ and L Ｖ The metallocene compound according to claim 1 or 2, characterized in that the group is the same and selected from hydrogen, chlorine, methyl group, phenyl group, benzyl group, and dimethylamine group.

4. A method for producing a metallocene compound according to any one of claims 1 to 3, The aforementioned manufacturing method is S1. H ２ (Cp ＩＩＩ ) is reacted with an alkali metal organic compound to obtain the corresponding [H(Cp ＩＩＩ )] － To produce alkali metal salts, S2. [H(Cp ＩＩＩ )] － Alkali metal salts R Ｉ R ＩＩ ZX ２ And it reacts to R Ｉ R ＩＩ Z[H(Cp ＩＩＩ )] ２ To generate, S3. R Ｉ R ＩＩ Z[H(Cp ＩＩＩ )] ２ The corresponding R is obtained by reacting it with an alkali metal organic compound. Ｉ R ＩＩ Z(Cp ＩＩＩ ) ２ ２- To produce alkali metal salts, S4. R Ｉ R ＩＩ Z(Cp ＩＩＩ ) ２ ２- Alkali metal salt X ２ ML ＩＶ L Ｖ This generates a salt removal reaction, R Ｉ R ＩＩ Z(Cp ＩＩＩ ) ２ ML ＩＶ L Ｖ To see, including, Here, X is selected from Cl, Br, and I, and the manufacturing method.

5. In S4, R Ｉ R ＩＩ Z(Cp ＩＩＩ ) ２ ２- There is no need to separate the alkali metal salt, and the salt removal reaction is directly generated with X ２ ML ＩＶ L Ｖ The production method according to claim 4

6. A method for producing a metallocene compound according to any one of claims 1 to 3, Precursor R Ｉ Hz (Cp ＩＩＩ ) ｎ (E) ２－ｎ ML ＩＶ L Ｖ and R ＩＩ The process involves producing the product by performing a Z hydrogenation reaction using a precursor, where n is 2. Here, R ＩＩ The precursor is a multibond-containing molecule, and the multibond-containing molecule is an organic multibond molecule, CO and CO ２ A method of production in which elements are selected from, where the multiple bonds are selected from elements of group 13 to 16, either homoatomic or heteroatomic.

7. The manufacturing method according to claim 6, wherein the multiple bond is one or more of the following bonds: 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.

8. The Z hydrogenation reaction is carried out in the presence of a catalyst, and the catalyst is selected from one or more types selected from transition metal catalysts and Lewis acid catalysts. and / or, the amount of catalyst used in the Z hydrogenation reaction is 0.00001 to 50% of the total mass of the reactants. And / or, the temperature of the Z hydrogenation reaction is -30 to 140°C. And / or, the reaction time of the Z hydrogenation reaction is greater than 0.1 h. The method for producing the precursor according to claim 6 or 7, wherein the obtained precursor is separated or purified by recrystallization, the solvent for recrystallization is an aprotic solvent selected from one or more linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds.

9. The catalyst is a platinum catalyst in a transition metal and B(C) in Lewis acid. ６ F ５ ) ３ One or more catalysts are selected, and / or The amount of catalyst used in the Z hydrogenation reaction is 0.01 to 20% of the total mass of the reactants, and / or The temperature of the Z hydrogenation reaction is 0 to 90°C, and / or The reaction time of the Z hydrogenation reaction is greater than 2 to 50 hours, and / or The manufacturing method according to claim 8, characterized in that the solvent for recrystallization is selected from one or more of toluene, xylene, hexane, heptane, cyclohexane, and methylcyclohexane.

10. The aforementioned precursor R Ｉ Hz (Cp ＩＩＩ ) ｎ (E) ２－ｎ ML ＩＶ L Ｖ It is manufactured by a one-pot chemical reaction. The aforementioned precursor R Ｉ Hz (Cp ＩＩＩ ) ｎ (E) ２－ｎ ML ＩＶ L Ｖ The manufacturing method is Step (1), H ２ (Cp ＩＩＩ ) is reacted with an alkali metal organic compound to obtain the corresponding [H(Cp ＩＩＩ )] － To produce alkali metal salts, Step (2), [H(Cp ＩＩＩ )] － Alkali metal salts R Ｉ HZX ２ And it reacts to R Ｉ Hz[H(Cp ＩＩＩ )] ２ To generate, Step (3), R Ｉ Hz[H(Cp ＩＩＩ )] ２ There is no need to separate them, directly L ｖｉｉｉ L ｖｉｖ ML ＩＶ L Ｖ It reacts with the stable small molecule L ｖｉｉｉ or L ｖｉｖ Detach the precursor R Ｉ Hz (Cp ＩＩＩ ) ２ ML ＩＶ L Ｖ To obtain and / or, R Ｉ Hz[H(Cp ＩＩＩ )] ２ There is no need to separate them, and they are directly reacted with alkali metal organic compounds to produce alkali metal salts, and the resulting alkali metal salt is further X ２ ML ＩＶ L Ｖ The salt removal reaction is carried out, and the precursor R Ｉ Hz (Cp ＩＩＩ ) ２ ML ＩＶ L Ｖ To see, including, The manufacturing method according to any one of claims 6 to 9, characterized in that, here, X is selected from Cl, Br, and I.

11. The manufacturing method according to any one of claims 4 to 10, characterized in that, in each step, the reaction temperature of the reaction is -100°C to 140°C, and / or the reaction time is greater than 0.016 h.

12. The manufacturing method according to any one of claim 11, characterized in that in each step, the reactants are mixed at a temperature of -100°C to -20°C, and the mixed reactants are reacted at a temperature of 10°C to 50°C for 1 to 100 hours.

13. In each step, the reaction is carried out in an aprotic solvent, the aprotic solvent being one or more selected from linear or branched alkane compounds, cycloalkane compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds and cyclic ether compounds. and / or, the alkali metal organic compound is selected from metal hydrides, alkyl metals, alkenyl metals, aromatic metals and amine metals. and / or, the manufacturing method according to any one of claims 4 to 12, characterized in that the alkali metal is selected from Li, Na, and K.

14. The aprotic solvent is selected from one or more of toluene, xylene, chlorobenzene, heptane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, tetrahydrofuran, ether, and dioxane. and / or, the alkali metal organic compound is C １ ~C ６ Selected from alkyl metals, The manufacturing method according to claim 13, characterized in that the alkali metal is Li.

15. A catalyst for α-olefin polymerization reaction comprising a metallocene compound, a co-catalyst, and a support according to any one of claims 1 to 3.

16. The catalyst according to claim 15, characterized in that the co-catalyst is one or more selected from a Lewis acid and an ionic compound containing a non-coordinating anion and a Lewis acid or Brønsted acid cation.

17. The catalyst according to claim 16, wherein the Lewis acid comprises one or more of alkylaluminum, alkylaluminoxane, and organoborides, and / or the ionic compound containing the non-coordinating anion and the Lewis acid or Brønsted acid cation is selected from compounds containing a borate anion substituted with one to four perfluoroaryl groups.

18. The alkylaluminum includes trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, triisohexylaluminum, tri-n-hexylaluminum, triisoheptylaluminum, tri-n-heptylaluminum, triisooctylaluminum, tri-n-octylaluminum, triisononylaluminum, tri-n-nonylaluminum, triisodecylaluminum and tri-n-decylaluminum, and / or the alkylaluminoxane includes methylaluminoxane, ethylaluminoxane and butyl-modified aluminoxane, and / or the organoboride includes trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and tris(2,4,6-trifluorophenyl)borane, and / or The catalyst according to claim 17, characterized in that 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.

19. The catalyst according to any one of claims 15 to 18, characterized in that the content of the metallocene compound is 0.001% to 10% by mass of element M, and / or the molar ratio of element Al in the co-catalyst to element M in the metallocene compound is (1 to 500):

1.

20. A method for producing a catalyst according to any one of claims 15 to 19, A method for producing a catalyst, comprising bonding the metallocene compound, the co-catalyst, and the support under the action of a solvent to form the catalyst.

21. The manufacturing method according to claim 20, wherein the bonding conditions include a bonding temperature of -40°C to 200°C and a bonding time greater than 0.016h.

22. The manufacturing method according to claim 20 or 21, characterized in that the solvent is one or more selected from linear hydrocarbon compounds, branched hydrocarbon compounds, cyclic saturated hydrocarbon compounds, and aromatic hydrocarbon compounds.

23. The manufacturing method according to claim 22, characterized in that the solvent 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.

24. Use of the metallocene compound according to any one of claims 1 to 3 or the catalyst according to any one of claims 15 to 19 in the field of α-olefin polymerization.

25. The use according to claim 24, characterized in that a polymerization reaction is carried out with an α-olefin in the presence of a metallocene compound according to any one of claims 1 to 3 or a catalyst according to any one of claims 15 to 19 to obtain a poly-α-olefin.

26. The use according to claim 25, characterized in that the polymerization reaction is carried out under conditions without a solvent.

27. The use according to any one of claims 24 to 26, characterized in that the conditions for the polymerization reaction are a reaction temperature of -50°C to 200°C and a reaction time of 0.01 h to 60 h.

28. The use according to any one of claims 24 to 27, characterized in that the amount of the metallocene catalyst or metallocene catalyst system used per gram of α-olefin is 0.001 mg to 1000 mg.

29. The α-olefin is C ２ ~C ２０ The use according to any one of claims 24 to 28, characterized by containing an α-olefin.

30. The use according to claim 29, characterized in that the α-olefin is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.

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