Pyridylamine-IVB group binuclear organometal complex, preparation method therefor, and use thereof

Abstract

The present invention relates to the technical field of olefin polymerization catalysts, and provides a pyridylamine-IVB group binuclear organometal complex, a preparation method therefor, and the use thereof. The structural formula of the pyridylamine-IVB group binuclear organometal complex is represented by formula (I). When applied to olefin polymerization, the pyridylamine-IVB group binuclear organometal complex has higher polymerization activity under similar polymerization conditions, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained in the comparative example, the molecular weight distribution of the obtained polymer is wide, and the molecular weight of the catalyzed polymerization product presents a bimodal distribution.

Description

A pyridine amine group ⅣB group binuclear metal organic complex and a preparation method and application thereof

[0001] Cross-reference to Related Applications

[0002] This application claims the benefit of Chinese Patent Application No. 202411026039.0, filed July 29, 2024, Chinese Patent Application No. 202411246382.6, filed September 5, 2024, Chinese Patent Application No. 202411823991.3, filed December 11, 2024, and Chinese Patent Application No. 202411824088.9, filed December 11, 2024, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the technical field of olefin polymerization catalysts, in particular to a pyridine amine group ⅣB group binuclear metal organic complex and a preparation method and application thereof. BACKGROUND

[0004] Polyolefin resins have excellent environmental compatibility compared to other resin materials, and are widely used in industry and daily life. Polyethylene resin is an important polyolefin resin. Industrialized polyethylene catalysts include Ziegler-Natta type catalysts (see, for example, DE Pat 889229 (1953); IT Pat 545332 (1956) and IT Pat 536899 (1955); Chem. Rev., 2000, 100, 1169 and related literature in the special issue), Phillips type catalysts (for example, Belg. Pat. 530617 (1955); Chem. Rev. 1996, 96, 3327) and metallocene type catalysts (for example, W. Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999) and high-efficiency ethylene oligomerization and polymerization catalysts of late transition metal complexes which have developed rapidly in recent years. In recent years, Dow Company has reported research on Group IVB metal complexes based on imine-amine ligands for catalyzing ethylene / α-olefin copolymerization, in which the complexes shown in formula 1 and formula 2 have isomerization at a relatively high temperature (Organometallics 2011, 30(2), 251-262, Organometallics 2013, 32(21), 6488-6499), have multiple active centers, although the molecular weight of the polymerization product is relatively high, but the insertion rate of 1-octene is low, and it is difficult to meet the basic requirements of elastomers. Compared with the former, the complex of 8-aminquinoline (shown in formula 3, Organometallics 2012, 31, 6244) has a relatively low catalytic activity, but the insertion rate of 1-octene is improved, but the reported polymerization reaction temperature is relatively low, which is difficult to meet the requirements of the solution polymerization process in industry; and in some applications of POE, such as PP toughening for automobiles, the requirement for the flowability of POE is increasing, and based on the current market situation, developing POE with high flowability and high melt index has become one of the new directions of research. SUMMARY

[0005] The purpose of the present application is to overcome the problems existing in the prior art, and to provide a pyridine amine-based Group IVB binuclear metal organic complex, which is relatively simple to synthesize, and has high catalytic activity when used as a main catalyst for olefin polymerization, and the olefin polymer prepared has high molecular weight and a wide molecular weight distribution range.

[0006] In order to achieve the above object, the present application provides a pyridine amine group ⅣB group double nuclear metal organic complex in one aspect, the structural formula of the pyridine amine group ⅣB group double nuclear metal organic complex is as shown in formula (I);

[0007] Wherein, R1 and R2 are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, C3-C30 cycloalkoxy, substituted or unsubstituted C6-C30 aryl and C6-C40 aryloxy;

[0008] R3-R7 are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 dialkylamino, substituted or unsubstituted C3-C30 cycloalkoxy, substituted or unsubstituted C4-C30 dicycloalkylamino, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C7-C40 aryloxy, substituted or unsubstituted C6-C40 arylamino and substituted or unsubstituted C3-C40 trialkylsilyl, or any two or more of R3-R7 are connected to form a cyclic structure;

[0009] X is selected from a divalent substituted group having 1-40 atoms, halogen or C1-C20 hydrocarbon group;

[0010] n is 1 or 2;

[0011] M is selected from ⅣB group metal.

[0012] The second aspect of the present application provides a method for preparing the above-mentioned pyridine amine group ⅣB group double nuclear metal organic complex, which comprises: carrying out a first reaction of a compound shown in formula (II) with a hydrogen abstraction agent in the presence of an organic solvent, then adding a M salt to carry out a second reaction, and then optionally adding a formate reagent to react;

[0013] Wherein, the M salt is a halide of IVB group metal and / or a hydrocarbon compound of IVB group metal; R1-R7 are defined as described above. Preferably, the method for preparing the compound shown in formula (II) comprises the following steps:

[0014] (1) carrying out a third reaction of a compound shown in formula (V) and a compound shown in formula (IV) in the presence of a first solvent and formic acid and / or acetic acid to obtain a compound shown in formula (III);

[0015] (2) carrying out a fourth reaction of the compound shown in formula (III) and compound A in the presence of a second solvent;

[0016] Wherein, compound A is LiR1 and / or Al(R1)3; the definitions of R1 to R7 are the same as those described above.

[0017] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising a main catalyst and a co-catalyst, wherein the main catalyst is the above-mentioned pyridine-amino group IVB binuclear metal-organic complex.

[0018] A fourth aspect of the present invention provides a method for olefin polymerization, comprising carrying out an olefin polymerization reaction in the presence of the catalyst described above for olefin polymerization.

[0019] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0020] (1) The method for synthesizing pyridine amino group IVB binuclear organometallic complexes described in this invention is simple and easy to implement;

[0021] (2) The catalyst for olefin polymerization prepared by the pyridine amino group IVB binuclear metal-organic complex described in this invention has high catalytic activity and can achieve near-living polymerization. The catalyzed olefin polymer has a high molecular weight and the molecular weight distribution of the catalyzed olefin polymer can be effectively controlled. The molecular weight distribution range is relatively wide (3≤PDI≤40). At the same time, the molecular weight of the catalyzed olefin polymer can show an obvious bimodal distribution.

[0022] (3) The olefin polymerization catalyst using the pyridine amino group IVB binuclear metal-organic complex described in this invention as the main catalyst also has high catalytic activity for olefin homopolymerization and copolymerization at high temperatures of 100°C and above.

[0023] (4) The catalyst for olefin polymerization using the pyridine amino group IVB binuclear metal-organic complex described in this invention as the main catalyst has high catalytic activity and can catalyze olefin homopolymerization, ethylene / α-olefin copolymerization, and especially ethylene copolymerization with higher α-olefins. Detailed Implementation

[0024] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0025] The structural formula of the pyridine-amino group IVB binuclear organometallic complex of the present invention is shown in formula (I).

[0026] R1 and R2 are each independently selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, C3-C30 cycloalkoxy, substituted or unsubstituted C6-C30 aryl and C6-C40 aryloxy.

[0027] R3to R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1to C30alkyl, substituted or unsubstituted C3to C30cycloalkyl, substituted or unsubstituted C1to C30alkoxy, substituted or unsubstituted C2to C30dialkylamino, substituted or unsubstituted C3to C30cycloalkoxy, substituted or unsubstituted C4to C30dicycloalkylamino, substituted or unsubstituted C6to C40aryl, substituted or unsubstituted C7to C40aryloxy, substituted or unsubstituted C6to C40arylamino, and substituted or unsubstituted C3to C40trihydrocarbylsilyl, or any two or more of R3to R7are joined to form a ring structure;

[0028] X is selected from the group consisting of a divalent substituent having 1 to 40 atoms, halogen, and C1to C20hydrocarbyl;

[0029] n is 1 or 2;

[0030] M is selected from the group consisting of Group IVB metals.

[0031] In preferred embodiments, R1and R2are each independently selected from the group consisting of hydrogen, C1to C20alkyl, C1to C20alkoxy, C3to C20cycloalkyl, C3to C20cycloalkoxy, substituted or unsubstituted C6to C30aryl, and C6to C30aryloxy; in more preferred embodiments, R1and R2are each independently selected from the group consisting of hydrogen, C1to C12alkyl, C1to C12alkoxy, C3to C12cycloalkoxy, substituted or unsubstituted C6to C24aryl, and C6to C24aryloxy; in still more preferred embodiments, R1and R2are each independently selected from the group consisting of hydrogen, C1to C6alkyl, phenyl, substituted C7to C20phenyl, naphthyl, substituted C7to C20naphthyl, anthryl, indenyl, fluorenyl, phenoxy, substituted C7to C20phenoxy, or substituted C7to C20naphthoxy.

[0032] In further preferred embodiments, R1and R2are not both hydrogen.

[0033] In one embodiment, when R2is hydrogen, R1is selected from the group consisting of substituted or unsubstituted C1-C30alkyl, C1-C30alkoxy, substituted or unsubstituted C3-C30cycloalkyl, C3-C30cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C40aryloxy, preferably R2is selected from the group consisting of C1-C20alkyl, C1-C20alkoxy, C3-C20cycloalkyl, C3-C20cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C30aryloxy; more preferably R2is selected from the group consisting of C1-C20alkyl, C1-C20alkoxy, C3-C20cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C30aryloxy; and even more preferably R2is selected from the group consisting of C1-C6alkyl, phenyl, substituted C7-C20phenyl, naphthyl, substituted C7-C20naphthyl, anthryl, indenyl, fluorenyl, phenoxy, substituted C7-C20phenoxy, or substituted C7-C20naphthoxy.

[0034] Based on the above embodiment, the structure of the pyridine amine group ⅣB group binuclear metal organic complex is shown as formula (VI),

[0035] wherein R1, R3-R7, X and n are defined as described above.

[0036] In another embodiment, R1and R2are each independently selected from the group consisting of substituted or unsubstituted C1-C30alkyl, C1-C30alkoxy, substituted or unsubstituted C3-C30cycloalkyl, C3-C30cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C40aryloxy, preferably R1and R2are each independently selected from the group consisting of C1-C20alkyl, C1-C20alkoxy, C3-C20cycloalkyl, C3-C20cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C30aryloxy; more preferably R1and R2are each independently selected from the group consisting of C1-C20alkyl, C1-C20alkoxy, C3-C20cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C30aryloxy; and even more preferably R1and R2are each independently selected from the group consisting of C1-C6alkyl, phenyl, substituted C7-C20phenyl, naphthyl, substituted C7-C20naphthyl, anthryl, indenyl, fluorenyl, phenoxy, substituted C7-C20phenoxy, or substituted C7-C20naphthoxy.

[0037] In preferred embodiments, R3to R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1to C20alkyl, C1to C20alkoxy, C2to C20dialkylamino, substituted or unsubstituted C3to C20cycloalkyl, C3to C20cycloalkoxy, C4to C20dicycloalkylamino, substituted or unsubstituted C6to C30aryl, C7to C30aryloxy, C6to C30arylamino, and C3to C30trihydrocarbylsilyl, or any two or more of R3to R7are joined together to form a ring structure; in more preferred embodiments, R3to R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1to C20alkyl, substituted or unsubstituted C3to C20cycloalkyl, and substituted or unsubstituted C6to C30aryl, or any two or more of R3to R7are joined together to form a ring structure; in further preferred embodiments, R3to R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1to C12alkyl, substituted or unsubstituted C3to C16cycloalkyl, and substituted or unsubstituted C6to C24aryl, or any two or more of R3to R7are joined together to form a ring structure; in still further preferred embodiments, R3to R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1to C6alkyl, substituted or unsubstituted C3to C12cycloalkyl, and substituted or unsubstituted C6to C20aryl.

[0038] In preferred embodiments, when n is 1, X is a divalent substituent having 1 to 40 atoms; when n is 2, X is a halogen or a C1to C20hydrocarbyl.

[0039] In more preferred embodiments, when n is 1, X is selected from the group consisting of an alkylene having 1 to 20 atoms, an arylene having 1 to 20 atoms, a diaminylene having 1 to 20 atoms, or a diene having 1 to 20 atoms; when n is 2, X is selected from the group consisting of a halogen, a substituted or unsubstituted C1to C10alkyl, and a substituted or unsubstituted C6to C10aryl.

[0040] According to some embodiments of the present application, when n is 1, X is 1,3- butadiene or 1,3-pentadiene; when n is 2, X is selected from the group consisting of a halogen, a methyl group, a benzyl group, or a phenyl group.

[0041] In preferred embodiments, M is selected from the group consisting of titanium, zirconium, or hafnium.

[0042] In the present application, “substituted or unsubstituted” in “substituted” means containing a substituent, which can be selected from the group consisting of a halogen, a hydroxyl group, a C1to C6alkyl group, a halogenated C1to C6alkyl group, a C1to C6alkoxy group, or a halogenated C1to C6alkoxy group.

[0043] In the present application, alkyl refers to straight-chain alkyl, branched-chain alkyl or cyclic alkyl, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

[0044] In the present application, alkyl (such as C1-C20 alkyl or C1-C6 alkyl) can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or 3,3-dimethylbutyl.

[0045] In the present application, alkoxy (such as C1-C6 alkoxy or C1-C20 alkoxy) can be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy or 3,3-dimethylbutoxy.

[0046] In the present application, aryl (such as C6-C30 aryl) can be selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 2-methylphenyl, 2-isopropylphenyl or vinylphenyl.

[0047] In the present application, the halogen is selected from fluorine, chlorine, bromine or iodine.

[0048] In a further preferred embodiment, the Group IVB dinuclear metal organic complex of pyridylamine is selected from the group consisting of:

[0049] Complex 1: the complex shown in formula (I), wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is Cl, and n is 2;

[0050] Complex 2: the complex shown in formula (I), wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are ethyl, R4-R6 are H, M is Hf, X is Cl, and n is 2;

[0051] Complex 3: the complex shown in formula (I), wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are methyl, R4-R6 are H, M is Hf, X is Cl, and n is 2;

[0052] Complex 4: the complex shown in formula (I), wherein R1 is phenyl, R2 is hydrogen, R3, R5 and R7 are methyl, R4 and R6 are H, M is Hf, X is Cl, and n is 2;

[0053] Complex 5: the complex shown in formula (I), wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are phenyl, R4-R6 are H, M is Hf, X is Cl, and n is 2.

[0054] Complex 6: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0055] Complex 7: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0056] Complex 8: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0057] Complex 9: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0058] Complex 10: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0059] Complex 11: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2;

[0060] Complex 12: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0061] Complex 13: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0062] Complex 14: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0063] Complex 15: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0064] Complex 16: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0065] Complex 17: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4- R6are H, M is Hf, X is benzyl, and n is 2;

[0066] Complex 18: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2;

[0067] Complex 19: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4- R6are H, M is Hf, X is benzyl, and n is 2;

[0068] Complex 20: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4- R6are H, M is Hf, X is benzyl, and n is 2;

[0069] Complex 21: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4- R6are H, M is Hf, X is benzyl, and n is 2;

[0070] Complex 22: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are isopropyl, R4- R6are H, M is Hf, X is Cl, and n is 2;

[0071] Complex 23: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are ethyl, R4- R6are H, M is Hf, X is Cl, and n is 2;

[0072] Complex 24: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are methyl, R4- R6are H, M is Hf, X is Cl, and n is 2;

[0073] Complex 25: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2;

[0074] Complex 26: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are phenyl, R4- R6are H, M is Hf, X is Cl, and n is 2;

[0075] Complex 27: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4- R6are H, M is Hf, X is Cl, and n is 2;

[0076] Complex 28: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0077] Complex 29: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0078] Complex 30: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0079] Complex 31 : A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0080] Complex 32: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2;

[0081] Complex 33: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0082] Complex 34: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0083] Complex 35: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0084] Complex 36: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0085] Complex 37: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0086] Complex 38: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0087] Complex 39: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2;

[0088] Complex 40: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0089] Complex 41 : A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0090] Complex 42: A complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0091] Complex 43: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0092] Complex 44: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0093] Complex 45: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0094] Complex 46: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2;

[0095] Complex 47: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0096] Complex 48: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0097] Complex 49: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0098] Complex 50: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0099] Complex 51 : a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0100] Complex 52: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0101] Complex 53: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2;

[0102] Complex 54: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0103] Complex 55: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0104] Complex 56: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0105] Complex 57: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0106] Complex 58: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0107] Complex 59: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0108] Complex 60: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2;

[0109] Complex 61 : A complex of Formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is benzyl, and n is 2.

[0110] Complex 62: A complex of Formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is benzyl, and n is 2.

[0111] Complex 63: A complex of Formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2.

[0112] Complex 64: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is Cl, and n is 2.

[0113] Complex 65: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is Cl, and n is 2.

[0114] Complex 66: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is Cl, and n is 2.

[0115] Complex 67: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2.

[0116] Complex 68: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is Cl, and n is 2.

[0117] Complex 69: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2.

[0118] Complex 70: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2.

[0119] Complex 71 : A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2.

[0120] Complex 72: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0121] Complex 73: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0122] Complex 74: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2;

[0123] Complex 75: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0124] Complex 76: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0125] Complex 77: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0126] Complex 78: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0127] Complex 79: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0128] Complex 80: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0129] Complex 81: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2;

[0130] Complex 82: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is benzyl, and n is 2;

[0131] Complex 83: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0132] Complex 84: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0133] Complex 85: A complex of formula (I) wherein R1, R3and R7are isopropyl, R2is hydrogen, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0134] Complex 86: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0135] Complex 87: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0136] Complex 88: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2;

[0137] Complex 89: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0138] Complex 90: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0139] Complex 91: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0140] Complex 92: A complex of formula (I) wherein R1, R3and R7are isopropyl, R2is hydrogen, R4to R6are H, M is Hf, X is methyl, and n is 2;

[0141] Complex 93: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4to R6are H, M is Hf, X is methyl, and n is 2;

[0142] Complex 94: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4- R6are H, M is Hf, X is methyl, and n is 2;

[0143] Complex 95: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2;

[0144] Complex 96: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4- R6are H, M is Hf, X is methyl, and n is 2;

[0145] Complex 97: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4- R6are H, M is Hf, X is methyl, and n is 2;

[0146] Complex 98: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are trifluoromethyl, R4- R6are H, M is Hf, X is methyl, and n is 2;

[0147] Complex 99: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4- R6are H, M is Zr, X is Cl, and n is 2;

[0148] Complex 100: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are ethyl, R4- R6are H, M is Zr, X is C, and n is 2;

[0149] Complex 101: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4- R6are H, M is Zr, X is Cl, and n is 2;

[0150] Complex 102: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is Cl, and n is 2;

[0151] Complex 103: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4- R6are H, M is Zr, X is Cl, and n is 2;

[0152] Complex 104: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4- R6are H, M is Zr, X is Cl, and n is 2;

[0153] Complex 105: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is Cl, and n is 2;

[0154] Complex 106: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0155] Complex 107: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0156] Complex 108: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0157] Complex 109: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2;

[0158] Complex 110: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0159] Complex 111: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0160] Complex 112: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0161] Complex 113: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is Cl, and n is 2;

[0162] Complex 114: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is Cl, and n is 2;

[0163] Complex 115: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is Cl, and n is 2;

[0164] Complex 116: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is Cl, and n is 2;

[0165] Complex 117: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0166] Complex 118: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0167] Complex 119: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0168] Complex 120: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0169] Complex 121: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0170] Complex 122: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0171] Complex 123: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2;

[0172] Complex 124: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0173] Complex 125: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0174] Complex 126: A complex according to formula (I) wherein R1is 2- isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0175] Complex 127: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0176] Complex 128: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0177] Complex 129: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0178] Complex 130: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2;

[0179] Complex 131: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0180] Complex 132: A complex of Formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0181] Complex 133: A complex of Formula (I) wherein R1, R3and R7are isopropyl, R2is hydrogen, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0182] Complex 134: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0183] Complex 135: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0184] Complex 136: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2;

[0185] Complex 137: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0186] Complex 138: A complex according to formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2.

[0187] Complex 139: A complex according to formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is methyl, and n is 2.

[0188] Complex 140: A complex according to formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0189] Complex 141: A complex according to formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0190] Complex 142: A complex according to formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0191] Complex 143: A complex according to formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Ti, X is methyl, and n is 2.

[0192] Complex 144: A complex according to formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0193] Complex 145: A complex according to formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0194] Complex 146: A complex according to formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0195] Complex 147: A complex according to formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0196] Complex 148: A complex according to formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Ti, X is methyl, and n is 2.

[0197] Complex 149: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Ti, X is methyl, and n is 2;

[0198] Complex 150: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Ti, X is methyl, and n is 2;

[0199] Complex 151 : A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Ti, X is methyl, and n is 2;

[0200] Complex 152: A complex of Formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Ti, X is methyl, and n is 2;

[0201] Complex 153: A complex of Formula (I) wherein R1and R2are methyl, R3and R7are isopropyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0202] Complex 154: A complex of Formula (I) wherein R1and R2are methyl, R3and R7are ethyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0203] Complex 155: A complex of Formula (I) wherein R1and R2are methyl, R3and R7are methyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0204] Complex 156: A complex of Formula (I) wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2;

[0205] Complex 157: A complex of Formula (I) wherein R1and R2are methyl, R3and R7are phenyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0206] Complex 158: A complex of Formula (I) wherein R1and R2are methyl, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0207] Complex 159: A complex of Formula (I) wherein R1and R2are methyl, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0208] Complex 160: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are isopropyl, R4to R6are H, M is Hf, X is methyl, and n is 2.

[0209] Complex 161 : A complex according to formula (I), wherein R1and R2are methyl, R3and R7are ethyl, R4to R6are H, M is Hf, X is methyl, and n is 2.

[0210] Complex 162: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are methyl, R4to R6are H, M is Hf, X is methyl, and n is 2.

[0211] Complex 163: A complex according to formula (I), wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2.

[0212] Complex 164: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are phenyl, R4to R6are H, M is Hf, X is methyl, and n is 2.

[0213] Complex 165: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is methyl, and n is 2.

[0214] Complex 166: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is methyl, and n is 2.

[0215] Complex 167: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are isopropyl, R4to R6are H, M is Hf, X is benzyl, and n is 2.

[0216] Complex 168: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are ethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2.

[0217] Complex 169: A complex according to formula (I), wherein R1and R2are methyl, R3and R7are methyl, R4to R6are H, M is Hf, X is benzyl, and n is 2.

[0218] Complex 170: A complex according to formula (I), wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2.

[0219] Complex 171 is a complex represented by formula (I), wherein R1and R2are methyl, R3and R7are phenyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0220] Complex 172 is a complex represented by formula (I), wherein R1and R2are methyl, R3and R7are cyclohexyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0221] Complex 173 is a complex represented by formula (I), wherein R1and R2are methyl, R3and R7are trifluoromethyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0222] Complex 174 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are isopropyl, R4~R6are H, M is Hf, X is Cl, and n is 2.

[0223] Complex 175 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are ethyl, R4~R6are H, M is Hf, X is Cl, and n is 2.

[0224] Complex 176 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are methyl, R4~R6are H, M is Hf, X is Cl, and n is 2.

[0225] Complex 177 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2.

[0226] Complex 178 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are phenyl, R4~R6are H, M is Hf, X is Cl, and n is 2.

[0227] Complex 179 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are cyclohexyl, R4~R6are H, M is Hf, X is Cl, and n is 2.

[0228] Complex 180 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are trifluoromethyl, R4~R6are H, M is Hf, X is Cl, and n is 2.

[0229] Complex 181 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are isopropyl, R4~R6are H, M is Hf, X is methyl, and n is 2.

[0230] Complex 182 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are ethyl, R4~R6are H, M is Hf, X is methyl, and n is 2.

[0231] Complex 183 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are methyl, R4~R6are H, M is Hf, X is methyl, and n is 2.

[0232] Complex 184 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2.

[0233] Complex 185 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are phenyl, R4~R6are H, M is Hf, X is methyl, and n is 2.

[0234] Complex 186 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are cyclohexyl, R4~R6are H, M is Hf, X is methyl, and n is 2.

[0235] Complex 187 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are trifluoromethyl, R4~R6are H, M is Hf, X is methyl, and n is 2.

[0236] Complex 188 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are isopropyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0237] Complex 189 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are ethyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0238] Complex 190 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are methyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0239] Complex 191 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2.

[0240] Complex 192 is a complex represented by formula (I), wherein R1is phenyl, R2is methyl, R3and R7are phenyl, R4~R6are H, M is Hf, X is benzyl, and n is 2.

[0241] Complex 193: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0242] Complex 194: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2;

[0243] Complex 195: A complex of formula (I) wherein R1and R2are methyl, R3and R7are isopropyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0244] Complex 196: A complex of formula (I) wherein R1and R2are methyl, R3and R7are ethyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0245] Complex 197: A complex of formula (I) wherein R1and R2are methyl, R3and R7are methyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0246] Complex 198: A complex of formula (I) wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is Cl, and n is 2;

[0247] Complex 199: A complex of formula (I) wherein R1and R2are methyl, R3and R7are phenyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0248] Complex 200: A complex of formula (I) wherein R1and R2are methyl, R3and R7are cyclohexyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0249] Complex 201: A complex of formula (I) wherein R1and R2are methyl, R3and R7are trifluoromethyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0250] Complex 202: A complex of formula (I) wherein R1and R2are methyl, R3and R7are isopropyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0251] Complex 203: A complex of formula (I) wherein R1and R2are methyl, R3and R7are ethyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0252] Complex 204: A complex of formula (I) wherein R1and R2are methyl, R3and R7are methyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0253] Complex 205: A complex of formula (I) wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2;

[0254] Complex 206: A complex of formula (I) wherein R1and R2are methyl, R3and R7are phenyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0255] Complex 207: A complex of formula (I) wherein R1and R2are methyl, R3and R7are cyclohexyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0256] Complex 208: A complex of formula (I) wherein R1and R2are methyl, R3and R7are trifluoromethyl, R4to R6are H, M is Zr, X is methyl, and n is 2;

[0257] Complex 209: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are isopropyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0258] Complex 210: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are ethyl, R4to R6are H, M is Zr, X is C, and n is 2;

[0259] Complex 211: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are methyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0260] Complex 212: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is Cl, and n is 2;

[0261] Complex 213: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are phenyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0262] Complex 214: A complex of formula (I) wherein R1is phenyl, R2is methyl, R3and R7are cyclohexyl, R4to R6are H, M is Zr, X is Cl, and n is 2;

[0263] Complex 215: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Zr, X is Cl, and n is 2;

[0264] Complex 216: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Zr, X is methyl, and n is 2;

[0265] Complex 217: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are ethyl, R4-R6 are H, M is Zr, X is methyl, and n is 2;

[0266] Complex 218: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are methyl, R4-R6 are H, M is Zr, X is methyl, and n is 2;

[0267] Complex 219: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Zr, X is methyl, and n is 2;

[0268] Complex 220: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are phenyl, R4-R6 are H, M is Zr, X is methyl, and n is 2;

[0269] Complex 221: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Zr, X is methyl, and n is 2;

[0270] Complex 222: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Zr, X is methyl, and n is 2;

[0271] Complex 223: a complex shown in formula (I), wherein R1 and R2 are methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Ti, X is methyl, and n is 2;

[0272] Complex 224: a complex shown in formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Ti, X is methyl, and n is 2.

[0273] The second application of the present application provides a method for preparing the above-mentioned pyridylamine group ⅣB double nuclear metal organic complex, which comprises:

[0274] a first reaction of a compound of formula (II) with a hydrogen abstractor in the presence of an organic solvent, followed by a second reaction with a M salt, and optionally a third reaction with a Grignard reagent;

[0275] wherein the M salt is a halide of a Group IVB metal and / or a hydrocarbyl compound of a Group IVB metal; and R1 to R7 are as defined above.

[0276] In the method for preparing the above-mentioned pyridine amine-based Group IVB dinuclear metal organic complex, there is no special requirement for the organic solvent, and any organic solvent commonly used in the art can be used. In a preferred embodiment, the organic solvent is selected from one or more of tetrahydrofuran, diethyl ether, pentane, cyclopentane, n-hexane, cyclohexane, heptane, methylcyclohexane, toluene, xylene, chlorobenzene and o-dichlorobenzene.

[0277] In a preferred embodiment, in order to improve the yield of the complex of formula (I), the first reaction is carried out at a temperature of -78 to 35°C for 1 to 24 hours; preferably, at a temperature of -78 to 20°C for 1 to 24 hours; specifically, the temperature can be -78°C, -50°C, -20°C, 0°C or 20°C; and the time can be 1 hour, 5 hours, 10 hours, 15 hours, 20 hours or 24 hours.

[0278] In a preferred embodiment, in order to further improve the yield of the complex of formula (I), the molar ratio of the compound of formula (II) to the hydrogen abstractor is 1:2 to 5, preferably 1:2 to 4.6; specifically, the molar ratio of the compound of formula (II) to the hydrogen abstractor can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4 or 1:4.6.

[0279] In a preferred embodiment, the hydrogen abstractor is selected from one or more of sodium hydride, potassium hydride, lithium hydride, tetramethylethylenediamine, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, lithium diisopropylamide and C1-C6 alkyl lithium.

[0280] In a preferred embodiment, in order to improve the yield of the complex of formula (I), the second reaction is carried out at a temperature of 60 to 120°C for 1 to 30 hours; preferably, at a temperature of 70 to 120°C for 1 to 12 hours; specifically, the temperature can be 70°C, 80°C, 90°C, 100°C, 110°C or 120°C; and the time can be 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours or 12 hours.

[0281] In a preferred embodiment, in order to further improve the yield of the complex shown in formula (I), the molar ratio of the compound shown in formula (II) to the metal M in the M salt is 1:2-3, preferably 1:2-2.6; specifically, the molar ratio of the compound shown in formula (II) to the metal M in the M salt can be 1:2, 1:2.2, 1:2.4 or 1:2.6.

[0282] In a preferred embodiment, the M salt is selected from halides of titanium, hydrocarbyl compounds of titanium, halides of zirconium, hydrocarbyl compounds of zirconium, halides of hafnium or hydrocarbyl compounds of hafnium.

[0283] In a specific embodiment, the M salt is selected from hafnium tetrachloride, zirconium tetrachloride, titanium tetrachloride, hafnium tetrabenzyl, zirconium tetrabenzyl or titanium tetrabenzyl.

[0284] In a preferred embodiment, the method for preparing the pyridyl amine-based Group IVB binuclear metal organic complex described above comprises:

[0285] In the presence of an organic solvent, the compound shown in formula (II) is subjected to a first reaction with a deprotonating agent, and then subjected to a second reaction with an M salt;

[0286] wherein the M salt is a halide of a Group IVB metal and / or a hydrocarbyl compound of a Group IVB metal; R1-R7 are defined as described above. In an embodiment, the reaction process for preparing the pyridyl amine-based Group IVB binuclear metal organic complex described above is shown in the following reaction formula:

[0287] wherein the M salt is a halide of a Group IVB metal and / or a hydrocarbyl compound of a Group IVB metal; M, X, n, R1-R7 are defined as described above.

[0288] In a specific embodiment, the preparation process of the pyridyl amine-based Group IVB binuclear metal organic complex described above comprises: in the presence of an organic solvent (e.g., toluene), the compound shown in formula (II) is subjected to a first reaction with a deprotonating agent (e.g., n-butyllithium), and then subjected to a second reaction with an M salt (e.g., hafnium tetrachloride), filtered, dried toluene is removed and washed with dry n-hexane to obtain the complex shown in formula (I).

[0289] In another embodiment, the method for preparing the pyridyl amine-based Group IVB binuclear metal organic complex described above, wherein X is not halogen, comprises:

[0290] In the presence of an organic solvent, the compound shown in formula (II) is subjected to a first reaction with a deprotonating agent, followed by a second reaction with an M salt, and then subjected to a reaction with a Grignard reagent;

[0291] wherein the M salt is a halide of a Group IVB metal and / or a hydrocarbyl compound of a Group IVB metal; and R1-R7 are as defined above.

[0292] In the present application, the format reagent can be an alkyl format reagent, an alkenyl format reagent or an aryl format reagent. Specific examples of the alkyl format reagent can be selected from, but not limited to, methyl magnesium bromide and / or ethyl magnesium bromide. Specific examples of the alkenyl format reagent can be selected from, but not limited to, vinyl magnesium bromide and / or allyl magnesium chloride. Specific examples of the aryl format reagent can be selected from, but not limited to, phenyl magnesium bromide and / or benzyl magnesium bromide.

[0293] In a preferred embodiment, the reaction for preparing the above-mentioned pyridyl amine-based Group IVB dinuclear metal organic complex with X being non-halogen is shown in the following reaction formula:

[0294] wherein the M salt is a halide of a Group IVB metal and / or a hydrocarbyl compound of a Group IVB metal; and M, n, R1-R7 are as defined above, X is as defined above and X is non-halogen.

[0295] In a preferred embodiment, in order to improve the yield of the complex shown in formula (I), the molar ratio of the compound shown in formula (II) to the format reagent is 1:6-10; preferably 1:6-8; specifically, the molar ratio of the compound shown in formula (II) to the format reagent can be 1:6, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9, 1:7, 1:7.2, 1:7.4, 1:7.6, 1:7.8, 1:8.

[0296] In a preferred embodiment, in order to improve the yield of the complex shown in formula (I), the reaction conditions include: temperature is 20-80℃, time is 6-24h.

[0297] In a specific embodiment, the preparation process of the above-mentioned pyridyl amine-based Group IVB dinuclear metal organic complex includes: in the presence of an organic solvent (e.g. toluene), a first reaction of the compound shown in formula (II) with a deprotonating agent (e.g. n-butyllithium), followed by a second reaction with a M salt (e.g. hafnium tetrachloride), then adding a format reagent (e.g. methyl magnesium bromide), stirring at 25℃ for 12h, removing toluene, adding 15mL dry n-hexane, standing, filtering and washing with dry n-hexane, removing the filtrate, adding 15mL dry toluene, filtering to collect the filtrate, and removing the solvent to obtain the complex shown in formula (I).

[0298] In a preferred embodiment, the method for preparing the compound shown in formula (II) includes the following steps:

[0299] (1) performing a third reaction on the compound shown as formula (V) and the compound shown as formula (IV) in the presence of a first solvent and formic acid and / or acetic acid to obtain a compound shown as formula (III);

[0300] (2) performing a fourth reaction on the compound shown as formula (III) and compound A in the presence of a second solvent;

[0301] wherein the compound A is LiR1 and / or Al(R1)3; and R1-R7 are the same as described above.

[0302] In the method for preparing the compound shown as formula (II) provided in the application, in step (1), the reaction process of the third reaction is shown in the following reaction formula:

[0303] wherein R2-R7 are the same as described above.

[0304] In a preferred embodiment, in step (1), the conditions of the third reaction include that the temperature is 50-120℃ and the time is 4-24h; specifically, the temperature can be 50℃, 80℃, 100℃ or 120℃; and the time can be 4h, 8h, 12h, 16h, 20h or 24h.

[0305] In a preferred embodiment, in order to further improve the yield of the compound shown as formula (III), in step (1), the molar ratio of the amount of the compound shown as formula (V) to the amount of the compound shown as formula (IV) is 1:2-8; specifically, the molar ratio of the amount of the compound shown as formula (V) to the amount of the compound shown as formula (IV) can be 1:2, 1:2.5, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8.

[0306] In a preferred embodiment, in step (1), the first solvent is selected from one or two or more of methanol, ethanol, toluene, xylene, benzene, diethyl ether and tetrahydrofuran.

[0307] In a preferred embodiment, step (1) further comprises separating and purifying the material after the first reaction, and the separation and purification mode is column chromatography or recrystallization.

[0308] In a specific embodiment, the preparation process of step (1) comprises: dissolving the compound shown as formula (V) in a first solvent (e.g. methanol), adding a compound shown as formula (IV) (e.g. 2,6-diisopropylaniline) and formic acid at room temperature, stirring at 80°C for 4h, removing 2,6-diisopropylaniline and methanol by distillation under reduced pressure, then precipitating and washing with ethanol, and recrystallizing from dichloromethane / petroleum ether to obtain the compound shown as formula (III).

[0309] In the method for preparing the compound shown as formula (II) provided in the present application, in step (2), the reaction process of the fourth reaction is shown in the following reaction formula:

[0310] wherein, the definitions of R1-R7 are the same as described above.

[0311] In a preferred embodiment, in order to improve the yield of the compound shown as formula (II), in step (2), the conditions of the fourth reaction include: temperature of -78-120°C, and time of 0.5-24h; specifically, the temperature can be -78°C, -50°C, -20°C, 0°C, 10°C, 35°C, 50°C, 65°C, 80°C, 95°C, 110°C or 120°C; and the time can be 0.5h, 4h, 8h, 12h, 16h, 20h or 24h.

[0312] In a preferred embodiment, in order to further improve the yield of the compound shown as formula (II), in step (2), the molar ratio of the use amount of the compound shown as formula (III) to the compound A is 1:2-10; preferably 1:2-8; more preferably 1:2-6; specifically, the molar ratio of the use amount of the compound shown as formula (III) to the compound A can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5 or 1:6.

[0313] In a specific embodiment, the LiR1 can be phenyllithium, 2-isopropylphenyllithium, 2-methyl-phenyllithium or tert-butyllithium.

[0314] In a specific embodiment, the Al(R1)3 can be trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum or tri-tert-butylaluminum.

[0315] In a preferred embodiment, in step (2), the second solvent is selected from one or two or more of methanol, ethanol, toluene, xylene, benzene, diethyl ether and tetrahydrofuran.

[0316] In a preferred embodiment, step (2) further comprises separating and purifying the material after the second reaction, and the separation and purification mode is column chromatography or recrystallization.

[0317] In a specific embodiment, the preparation process of step (2) comprises: dissolving the compound of formula (III) in a second solvent (e.g. tetrahydrofuran) at room temperature under oxygen-free condition, adding LiR1(e.g. phenyllithium) dropwise at -78°C, after the addition is completed, warming to room temperature and stirring for 3h, adding ammonium chloride aqueous solution to terminate the reaction, then extracting the organic phase with ethyl acetate, and separating the organic phase by silica gel gel chromatography to obtain the compound of formula (II).

[0318] In another specific embodiment, the preparation process of step (2) comprises: dissolving the compound of formula (III) in a second solvent (e.g. toluene) at room temperature under oxygen-free condition, adding Al(R1)3(e.g. trimethylaluminum) dropwise at -78°C, after the addition is completed, warming to reflux and stirring for 3h, adding ammonium chloride aqueous solution to terminate the reaction, then extracting the organic phase with ethyl acetate, and separating the organic phase by silica gel gel chromatography to obtain the compound of formula (II).

[0319] The third aspect of the present application provides an olefin polymerization catalyst, which comprises a main catalyst and a cocatalyst, wherein the main catalyst is the above-mentioned pyridine amine-based group IVB binuclear metal organic complex; and the cocatalyst is selected from one or more than two of aluminoxane, alkylaluminum compound, chlorinated alkylaluminum, alkylzinc and optional organoboron compound.

[0320] In a preferred embodiment, the aluminoxane is methylaluminoxane and / or modified methylaluminoxane.

[0321] In a preferred embodiment, the alkylaluminum compound is selected from one or more than two of triethylaluminum, triisobutylaluminum and trioctylaluminum.

[0322] In a preferred embodiment, the chlorinated alkylaluminum is selected from one or more than two of monochloroethylaluminum, sesquiethylaluminum chloride and dichloroethylaluminum.

[0323] In a preferred embodiment, the organoboron compound is selected from one or more than two of triphenylmethyl tetra(pentafluorophenyl)borate, triphenylmethyl tetra(pentafluorophenyl)borate, tris(pentafluorophenyl)boron, N,N-dimethylaniline tetra(pentafluorophenyl)borate, dioctadecylmethyl tertiary amine tetra(pentafluorophenyl)borate and dihydrogenated tallowmethyl tertiary amine tetra(pentafluorophenyl)borate.

[0324] In a preferred embodiment, the molar ratio of aluminum metal in the cocatalyst to metal M in the main catalyst is 1-10000:1; and the molar ratio of boron element in the cocatalyst to metal M in the main catalyst is 0-10:1.

[0325] In more preferred embodiments, the molar ratio of the aluminum metal in the co-catalyst to the metal M in the main catalyst is 3 to 1000: 1; and the molar ratio of the boron element in the co-catalyst to the metal M in the main catalyst is 0 to 4: 1.

[0326] In specific embodiments, the molar ratio of the aluminum metal in the co-catalyst to the metal M in the main catalyst can be 3: 1, 10: 1, 100: 1, 500: 1, or 1000: 1; and the molar ratio of the boron element in the co-catalyst to the metal M in the main catalyst can be 0: 1, 1: 1, 2: 1, 3: 1, or 4: 1.

[0327] The fourth aspect of the present application provides a method for olefin polymerization, comprising performing an olefin polymerization reaction in the presence of the above-mentioned catalyst for olefin polymerization.

[0328] In preferred embodiments, the olefin is selected from the group consisting of ethylene and / or an α-olefin.

[0329] In more preferred embodiments, the α-olefin is selected from one or more than two of propylene, butene, pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene.

[0330] In preferred embodiments, the temperature of the polymerization reaction is -78°C to 250°C, more preferably -20°C to 200°C; and the polymerization pressure is 0.1 to 100 atm, more preferably 0.1 to 50 atm.

[0331] In specific embodiments, the temperature of the polymerization reaction can be -20°C, -10°C, 0°C, 50°C, 100°C, 120°C, 140°C, 160°C, 180°C, or 200°C; and the polymerization pressure can be 0.1 atm, 1 atm, 4 atm, 10 atm, 20 atm, or 50 atm.

[0332] In the present application, the "polymerization pressure" refers to the ethylene pressure in the polymerization system, expressed in absolute pressure.

[0333] According to some embodiments of the present application, the polymerization reaction is performed in a solvent, which is independently selected from one or more than two of alkanes, aromatic hydrocarbons, and halogenated hydrocarbons.

[0334] According to some specific embodiments of the present application, the polymerization solvent is independently selected from one or more than two of hexane, pentane, heptane, decane, benzene, toluene, dichloromethane, chloroform, and dichloroethane, more preferably one or more than two of hexane, decane, toluene, and heptane.

[0335] The pyridyl amine group ⅣB group binuclear metal organic complex, the preparation method and the application thereof are further illustrated by the following examples. The examples are implemented on the premise of the technical scheme of the present application, and the detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following examples.

[0336] In the following examples, the experimental methods are the conventional methods in the art, unless otherwise specified. The experimental materials used in the following examples are commercially available, unless otherwise specified.

[0337] (1) NMR instrument: Bruker DMX 300 (300 MHz), with tetramethylsilane (TMS) as an internal standard;

[0338] (2) Characterization of polymer molecular weight and molecular weight distribution: the molecular weight and its distribution are determined by gel permeation chromatography (GPC), using a PL-GPC220 chromatograph at 150°C, with 1,2,4-trichlorobenzene as a solvent for dissolving the polymer sample, wherein the sample concentration is 1 mg / mL, the solvent flow rate is 1.0 mL / min, the chromatographic column is 3xPLgel 10um M1xED-B 300x7.5nm, and each sample is measured twice;

[0339] (3) Activity measurement method: the polymer is washed with hydrochloric acid ethanol solution, vacuum dried, and the weight of the polymer is determined; the calculation method of polymerization activity is: polymer weight (g) / metal M (mol) x 60 / polymerization time (min);

[0340] (4) Complex structure analysis: single crystal test analysis, using a Rigaku RAXIS Rapid IP diffractometer;

[0341] (5) Analysis of comonomer content of the polymer: using 1 H NMR, 13 C NMR spectrum measurement, on a 400MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, using a 10mm PASEX 13 probe, dissolving the polymer sample in 1,2,4-trichlorobenzene at 120°C for analysis and testing.

[0342] Example 1

[0343] Complex 8: a complex represented by formula (I), wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is methyl, and n is 2;

[0344] The compound represented by formula (V) (10 g, 0.035 mol) was dissolved in methanol (200 mL) at room temperature under a nitrogen atmosphere, compound 2,6-diisopropylaniline (20 mL, 0.1 mol) and p-toluenesulfonic acid (0.6 g, 0.0035 mol) were added, and the mixture was stirred at 80°C for 16 h, then filtered and recrystallized with methanol for 3 times to obtain the compound represented by formula (III) III-1, with a yield of 58.0%; liquid chromatography test (LCMS): [M+H] + = 607.4; 1 H NMR (400 MHz, CDCl3) δ 8.78 (s, 1H), 8.44 (s, 2H), 8.28 (dd, J = 6.1, 2.5 Hz, 2H), 8.17 (dd, J = 7.7, 1.5 Hz, 2H), 7.98-7.91 (m, 4H), 7.64 (t, J = 7.8 Hz, 1H), 7.25-7.11 (m, 6H), 3.04-2.97 (m, 4H), 1.19 (d, J = 6.9 Hz, 24H);

[0345] The compound represented by formula (III) III-1 (36.38 g, 0.06 mol) was dissolved in ether (500 mL) at room temperature under anaerobic conditions, and 1M phenyllithium (200 mL, 0.2 mol) was added dropwise at -78°C, then the mixture was warmed to room temperature and stirred for 3 h, then the reaction was terminated by adding an aqueous solution of ammonium chloride, and the organic phase was extracted with ethyl acetate, and the organic phase was separated by silica gel gel chromatography to obtain the compound represented by formula (II) II-1, with a yield of 62.2%; LCMS: [M+H] + = 764.2; 1 H NMR (400 MHz, CDCl3) δ 8.74-8.67 (m, 1H), 8.21 (m, 2H), 7.67 (ddt, J = 15.7, 11.0, 5.3 Hz, 5H), 7.44 (dd, J = 6.9, 5.1 Hz, 4H), 7.26 (dd, J = 7.2, 5.8 Hz, 6H), 7.19 (dd, J = 7.8, 6.0 Hz, 2H), 7.12 (d, J = 7.3 Hz, 2H), 7.04-6.95 (m, 6H), 5.23 (d, J = 2.7 Hz, 2H), 3.32-3.16 (m, 4H), 1.08 (m, 12H), 1.00 (m, 12H);

[0346] In a glove box, 3.156 g of compound II-1 shown in formula (II) (4.13 mmol) was dissolved in 20 mL of dry toluene, 3.47 mL of n-butyllithium solution in hexane (8.68 mmol) was slowly added dropwise, after 1.5 h of reaction at 20 ℃, 2.64 g (8.26 mmol) of hafnium tetrachloride was added, and the temperature was increased to 120 ℃ and refluxed for 2 h; 9.6 mL (28.79 mmol) of methyl magnesium bromide was added, and stirred at 25 ℃ for 12 h, the toluene was pumped out, 15 mL of dry n-hexane was added, stirred for 15 min, and then allowed to stand, filtered and washed with dry n-hexane, the filtrate was pumped out, 15 mL of dry toluene was added again, the filtrate was collected by filtration, and the solvent was pumped out to obtain a yellow solid, which was complex 8, with a yield of 62.2%; 1 H NMR (400 MHz, C6D6): 9.06 (s, 1H), 9.00 (s, 1H), 6.5-7.6 (m, 22H), 5.89 (s, 1H), 5.96 (s, 1H), 3.82-3.11 (m, 4H), 1.55-1.17 (m, 12H), 1.02 (s, 3H), 0.75 (s, 6H), 0.70 (m, 6H), 0.55 (s, 3H), 0.39 (d, 3H), 0.30 (d, 3H); elemental analysis test C 58 H 66 Hf2N4; the theoretical calculation value is: C, 59.23; H, 5.66, N, 4.76; the test value is: C, 59.12; H, 5.88, N, 4.92;

[0347] A 1L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 ℃ for 3 h, while hot, vacuumized and replaced with N2for 3 times, 500 mL of dry hexane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.3 mg of complex 8 (2 μmol) were added, and the reaction was carried out at 60 ℃ under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60 ℃ to constant weight, and then weighed and analyzed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0348] Example 2

[0349] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. 500 mL of dried hexane was injected into the reactor, followed by the addition of 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) of complex 8. The reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, followed by venting of ethylene. The reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight before weighing and sample analysis. The test data of the obtained polymer, such as weight average molecular weight, molecular weight distribution and polymerization activity, are shown in Table 1.

[0350] Example 3

[0351] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. 500 mL of dried hexane was injected into the reactor, followed by the addition of 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) of complex 8. The reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, followed by venting of ethylene. The reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight before weighing and sample analysis. The test data of the obtained polymer, such as weight average molecular weight, molecular weight distribution and polymerization activity, are shown in Table 1.

[0352] Example 4

[0353] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. 500 mL of dried hexane was injected into the reactor, followed by the addition of 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) of complex 8. The reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, followed by venting of ethylene. The reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight before weighing and sample analysis. The test data of the obtained polymer, such as weight average molecular weight, molecular weight distribution and polymerization activity, are shown in Table 1.

[0354] Example 5

[0355] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 400 mL of dried decane was injected into the reactor, 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) of complex 8 were added, the reaction was carried out at 140°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60°C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0356] Example 6

[0357] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 400 mL of dried decane was injected into the reactor, 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) of complex 8 were added, the reaction was carried out at 140°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60°C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0358] Example 7

[0359] A 50 mL Schlenk reactor was dried by vacuuming for 2 h and replaced with N2for 3 times, 5 mL of dried toluene solution was added, 5 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) of complex 8 were added, the reaction was carried out at 40°C with vigorous stirring for 60 min, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60°C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0360] Example 8

[0361] 50 mL Schlenk tube was vacuum dried for 2 h and replaced with N2for 3 times, 5 mL dry toluene was added, 5 mL 1-decene, 1.0 mL triisobutylaluminum (1 mol / L toluene solution), 3.7 mg triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) complex 8 were added, the reaction was carried out at 40 °C for 60 min with vigorous stirring, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was carried out, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0362] Example 9

[0363] 50 mL Schlenk tube was vacuum dried for 2 h and replaced with N2for 3 times, 5 mL dry toluene was added, 5 mL 1-decene, 1.0 mL triisobutylaluminum (1 mol / L toluene solution), 3.7 mg triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (2 μmol) complex 8 were added, the reaction was carried out at 40 °C for 60 min with vigorous stirring, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was carried out, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0364] Example 10

[0365] Complex 50: a complex represented by formula (I), wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0366] Under anaerobic conditions, compound III-1 represented by formula (III) (36.38 g, 0.06 mol) was dissolved in diethyl ether (500 mL) at room temperature, 2-isopropylphenyllithium (0.36 mol) was added dropwise at -78 °C, after the addition was completed, the temperature was raised to room temperature and stirred for 3 h, then ammonium chloride aqueous solution was added to terminate the reaction, then the organic phase was extracted with ethyl acetate, and the organic phase was separated by silica gel gel chromatography to obtain compound II-2 represented by formula (II) with a yield of 65.1%; LCMS: [M+H] + = 847.6; 1H NMR (400 MHz, CDC13) δ 8.50 (d, J = 8.7 Hz, 1H), 8.06 (d, J = 7.7 Hz, 2H), 7.73 - 7.68 (m, 2H), 7.61 (dd, J = 11.0, 7.6 Hz, 4H), 7.52 (t, J = 7.7 Hz, 1H), 7.23 (d, J = 2.6 Hz, 6H), 7.10 (d, J = 7.1 Hz, 2H), 7.05 - 7.00 (m, 6H), 5.50 (s, 2H), 4.67 (s, 2H), 3.14 (dt, J = 13.5, 6.7 Hz, 2H), 3.02 (dq, J = 13.2, 6.6 Hz, 4H), 1.03 - 0.92 (m, 36H);

[0367] In a glove box, 3.052 g of compound II-2 (3.6 mmol) was dissolved in 20 mL of dry toluene, 3.04 mL of n-butyllithium in hexane (7.60 mmol) was added dropwise, and the reaction was carried out at 20 °C for 1.5 h. Then, 2.3 g of hafnium tetrachloride (7.2 mmol) was added, and the temperature was raised to 120 °C for reflux for 2 h. Then, 8.4 mL of methylmagnesium bromide (25.17 mmol) was added, and the reaction was carried out at 25 °C for 12 h. The toluene was removed by suction, 20 mL of dry n-hexane was added, and the mixture was stirred for 15 min. The mixture was filtered, and the filtrate was collected. The solvent was removed to obtain a brown-green solid, which was complex 50, with a yield of 65.2%. 1 H NMR (400 MHz, C6D6): 9.06 (s, 1H), 8.94 (s, 1H), 6.5-7.5 (m, 22H), 6.23 (m, 2H), 3.74-3.13 (m, 4H), 1.75-0.40 (m, 45H), 0.30 (d, 3H); Elemental Analysis Test C 64 H 78 Hf2N4; Theoretical calculation value: C, 60.99; H, 6.24; N, 4.45; Test value: C, 61.11; H, 6.38, N, 4.22;

[0368] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the reactor, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50 were added, the reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0369] Example 11

[0370] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the reactor, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50 were added, the reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0371] Example 12

[0372] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the reactor, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50 were added, the reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0373] Example 13

[0374] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. The reactor was charged with 500 mL of dried decane, 20 mL of 1-octene, 2.0 mL of methylaluminoxane (10 wt% in toluene) and 2.5 mg (2 μmol) of complex 50. The reaction was carried out at 120 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and then weighed and analyzed. The test data of the obtained polymer, such as weight average molecular weight, molecular weight distribution and polymerization activity, are shown in Table 1.

[0375] Example 14

[0376] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. The reactor was charged with 400 mL of dried decane, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L in hexane), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50. The reaction was carried out at 140 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and then weighed and analyzed. The test data of the obtained polymer, such as weight average molecular weight, molecular weight distribution and polymerization activity, are shown in Table 1.

[0377] Example 15

[0378] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. The reactor was charged with 300 mL of dried decane, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L in hexane), 3.7 mg of triphenylphosphonium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50. The reaction was carried out at 140 °C under 12 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and then weighed and analyzed. The test data of the obtained polymer, such as weight average molecular weight, molecular weight distribution and polymerization activity, are shown in Table 1.

[0379] Example 16

[0380] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed and replaced with N2for 3 times while hot, 300 mL of dried decane was injected into the polymerization kettle, 80 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.7 mg of triphenylmethyl tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50 were added, the reaction was carried out at 180 °C under 12 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0381] Example 17

[0382] A 50 mL Schlenk tube was dried by vacuum for 2 h and replaced with N2for 3 times, 5 mL of dried toluene solution was added, 5 mL of 1-octene, 0.5 mL of triisobutylaluminum (1 mol / L toluene solution), 1.6 mg of N,N-dimethylanilinium tetra(pentafluorophenyl)borate (2 μmol) and 1.2 mg (1 μmol) of complex 50 were added, the reaction was carried out at 25 °C with vigorous stirring for 60 min, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0383] Example 18

[0384] A 50 mL Schlenk tube was dried by vacuum for 2 h and replaced with N2for 3 times, 5 mL of dried toluene solution was added, 5 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylmethyl tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) of complex 50 were added, the reaction was carried out at 40 °C with vigorous stirring for 60 min, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0385] Example 19

[0386] 50 mL Schlenk tube was vacuumed and dried for 2 h, and replaced with N2for 3 times, 5 mL dry toluene was added, 5 mL 1-decene, 1.0 mL triisobutylaluminum (1 mol / L toluene solution), 3.7 mg triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) complex 50 were added, the reaction was carried out at 40 ℃ for 60 min with vigorous stirring, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60 ℃ to constant weight, and sample analysis was carried out, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0387] Example 20

[0388] 50 mL Schlenk tube was vacuumed and dried for 2 h, and replaced with N2for 3 times, 5 mL dry toluene was added, 5 mL 1-decene, 1.0 mL triisobutylaluminum (1 mol / L toluene solution), 3.7 mg triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.5 mg (2 μmol) complex 50 were added, the reaction was carried out at 40 ℃ for 60 min with vigorous stirring, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60 ℃ to constant weight, and sample analysis was carried out, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0389] Example 21

[0390] Complex 43: a complex represented by formula (I), wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is Cl, and n is 2;

[0391] In the glove box, 3.052 g of a compound represented by formula (II) II-2 (3.6 mmol) was dissolved in 20 mL of dry toluene, 3.04 mL of n-butyllithium hexane solution (7.60 mmol) was slowly added dropwise, and after reaction at 20 ℃ for 1.5 h, 2.30 g (7.2 mmol) of hafnium tetrachloride was added, and the temperature was increased to 120 ℃ and refluxed for 4 h, 20 mL of dry dichloromethane was added, stirred for 15 min, and then stood, filtered and washed with dry dichloromethane, the filtrate was concentrated, 30 mL of dry hexane was added, the filter cake was collected by filtration to obtain complex 43 with a yield of 70.3%; 1 H NMR (400 MHz, C6D6): 8.59 (s, 1H), 8.47 (s, 1H), 8.0-7.6 (m, 6H), 7.4-6.5 (14H), 5.50 (m, 2H), 3.92-3.00 (m, 6H), 1.40-0.87 (m, 30H), 0.50-0.34 (m, 6H); elemental analysis test C60 H 66 Cl4Hf2N4; Calc: C, 53.70; H, 4.96; N, 4.17; Found: C, 53.91; H, 5.24, N, 4.02;

[0392] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed and replaced with N2for 3 times, 500 mL of dried decane was injected into the reactor, 20 mL of 1-octene, 2.0 mL of methylaluminoxane (10 wt% toluene solution) and 2.7 mg (2 μmol) of complex 43 were added, the reaction was carried out at 120 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and then weighed and analyzed. The test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0393] Example 22

[0394] Complex 71: a complex represented by formula (I), wherein R1is tert-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2;

[0395] Under an oxygen-free condition, compound III-1 represented by formula (III) (36.38 g, 0.06 mol) was dissolved in diethyl ether (500 mL) at room temperature, 1 M tert-butyllithium (200 mL, 0.2 mol) was added dropwise at -78 °C, after the dropwise addition was completed, the temperature was raised to room temperature and stirred for 3 h, then an aqueous solution of ammonium chloride was added to terminate the reaction, then the organic phase was extracted with ethyl acetate, and the organic phase was separated by silica gel gel chromatography to obtain compound II-3 represented by formula (II) in a yield of 22.4%; LCMS: [M+H] + = 721.7; elemental analysis test C 50 H 66 N4; Calc: C, 83.05; H, 9.20; N, 7.75; Found: C, 83.21; H, 9.04, N, 7.52;

[0396] In a glove box, 2.954 g of compound II-3 shown in formula (II) (4.1 mmol) was dissolved in 20 mL of dry toluene, 3.6 mL of n-butyllithium hexane solution (9.02 mmol) was slowly added, after 1.5 h of reaction at 20 ℃, 2.62 g of hafnium tetrachloride (8.2 mmol) was added, and the temperature was increased to 120 ℃ and refluxed for 2 h; 9.6 mL of methyl magnesium bromide (28.7 mmol) was added, stirred at 25 ℃ for 12 h, the toluene was removed, 15 mL of dry n-hexane was added, stirred for 15 min, and then placed, filtered and washed with dry n-hexane, the filtrate was removed, 15 mL of dry toluene was added, the filtrate was collected by filtration, and the solvent was removed to obtain a yellow solid, which was complex 71, with a yield of 53.1%; elemental analysis test C 54 H 74 Hf2N4; the theoretical calculation value is C, 57.08; H, 6.57; N, 4.93; the test value is C, 57.31; H, 6.84, N, 4.82;

[0397] A 1 L stainless steel polymerization kettle with mechanical stirring was continuously dried at 130 ℃ for 3 h, vacuumized while hot and replaced with N2 for 3 times, 500 mL of dry decane was injected into the polymerization kettle, 20 mL of 1-octene, 2.0 mL of methylaluminoxane (10 wt% toluene solution) and 2.3 mg (2 μmol) of complex 71 were added, and the reaction was carried out at 100 ℃ under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60 ℃ to constant weight, and then weighed and analyzed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0398] Example 23

[0399] Complex 53: a complex shown in formula (I), wherein R1 is 2-isopropylphenyl, R2 is hydrogen, R3, R5 and R7 are -CH3, R4 and R6 are H, M is Hf, X is methyl, and n is 2;

[0400] In a nitrogen atmosphere, the compound shown in formula (V) (synthesis reference J. Am. Chem. Soc. 2020, 142, 12, 5819-5824) (10 g, 0.035 mol) was dissolved in methanol (200 mL) at room temperature, compound 2,4,6-trimethylaniline (14.4 mL, 0.1 mol) and p-toluenesulfonic acid (0.6 g, 0.0035 mol) were added, the temperature was increased to 80 ℃ and refluxed and stirred for 18 h, then filtered and recrystallized with methanol for 3 times to obtain compound III-2 shown in formula (III) with a yield of 64.0%; liquid chromatography test (LCMS): [M+H] + = 523.1;

[0401] Compound III-2 shown in formula (III) III-2 (31.36 g, 0.06 mol) was dissolved in ether (500 mL) at room temperature under anaerobic condition, and 2-isopropylphenyllithium (0.36 mol) was added dropwise at -78 °C. After the addition was completed, the mixture was warmed to room temperature and stirred for 3 h. Then, the reaction was terminated by adding an aqueous solution of ammonium chloride, and the organic phase was extracted with ethyl acetate. The organic phase was separated by silica gel gel chromatography to obtain compound II-4 shown in formula (II) in a yield of 67.2%; LCMS: [M+H] = 763.2; elemental analysis test C + 54 H 58 N4; the theoretical calculation value was C, 85.00; H, 7.66; N, 7.34; the test value was C, 85.23; H, 7.82, N, 7.23;;

[0402] In a glove box, 3.052 g of compound II-4 shown in formula (II) II-4 (4.0 mmol) was dissolved in 20 mL of dry toluene, and 3.6 mL of n-butyllithium hexane solution (9.02 mmol) was added dropwise. After the reaction was carried out at 20 °C for 1.5 h, 2.56 g (8.0 mmol) of hafnium tetrachloride was added, and the mixture was warmed to 120 °C and refluxed for 2 h. Then, 9.6 mL (28.7 mmol) of methylmagnesium bromide was added, and the mixture was stirred at 25 °C for 12 h. After the toluene was removed, 15 mL of dry n-hexane was added, and the mixture was stirred for 15 min and then allowed to stand. The mixture was filtered and washed with dry n-hexane. The filtrate was removed, and 15 mL of dry toluene was added. The filtrate was collected by filtration, and the solvent was removed to obtain a yellow solid, which was complex 53 in a yield of 63.2%; elemental analysis test C 58 H 66 Hf2N4; the theoretical calculation value was C, 59.23; H, 5.66; N, 4.76; the test value was C, 59.42; H, 5.82, N, 4.63;;

[0403] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumized and replaced with N2 for 3 times. Then, 500 mL of dried decane, 20 mL of 1-octene, 2.0 mL of methylaluminoxane (10 wt% toluene solution) and 2.4 mg (2 μmol) of complex 53 were added into the polymerization kettle. The reaction was carried out at 100 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, and then the ethylene was released. The reaction solution was neutralized with 10 wt% hydrochloric acid ethanol solution, and the precipitated solid was collected and dried in a vacuum drying oven at 60 °C to constant weight. The weight of the polymer was measured, and the test data of the weight average molecular weight, the molecular weight distribution and the polymerization activity of the polymer were shown in Table 1.

[0404] Example 24 ​

[0405] Complex 106: a complex represented by formula (I), wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4~R6are H, M is Zr, X is methyl, and n is 2;

[0406] In a glove box, 2.178 g of compound II-1 represented by formula (II) II-1 (2.85 mmol) was dissolved in 10 mL of dry toluene, 2.6 mL of n-butyllithium hexane solution (6.54 mmol) was slowly added dropwise, after 1.5 h of reaction at 20 °C, 1.33 g (5.7 mmol) of zirconium tetrachloride was added, and the temperature was raised to 120 °C and refluxed for 2 h; 6.2 mL (18.6 mmol) of methyl magnesium bromide was added, and stirred at 25 °C for 12 h, the toluene was pumped out, 20 mL of dry n-hexane was added, stirred for 15 min, and then placed, filtered and washed with dry n-hexane, the filtrate was pumped out, 30 mL of dry toluene was added, the filtrate was collected by filtration, and the solvent was pumped out to obtain a brown-red solid, which was complex 106, with a yield of 68.3%; elemental analysis test C 64 H 78 Zr2N4; the theoretical calculation value is: C, 70.80; H, 7.24; N, 5.16; the test value is: C, 70.91; H, 7.39, N, 5.12;

[0407] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, and then vacuumized and replaced with N2for 3 times while hot, 500 mL of dry decane was injected into the polymerization kettle, 2.0 mL of methylaluminoxane (10 wt% toluene solution) and 2.0 mg (2 μmol) of complex 106 were added, and then the reaction was carried out at 100 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, and then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60 °C to constant weight, and then weighed and analyzed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0408] Example 25

[0409] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 ℃ for 3 h, and then vacuumed and replaced with N2 for 3 times. 500 mL of dried decane was injected into the reactor, followed by the addition of 20 mL of 1-octene, 2.0 mL of methylaluminoxane (10 wt% toluene solution), and 2.0 mg (2 μmol) of complex 106. The reaction was carried out at 120 ℃ under 10 atm of ethylene pressure with vigorous stirring for 30 min, and then the ethylene was released. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 ℃ to constant weight, and then weighed and analyzed. The test data of the weight average molecular weight, molecular weight distribution, and polymerization activity of the obtained polymer are shown in Table 1.

[0410] Example 26

[0411] Complex 160: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is methyl, and n is 2;

[0412] The compound represented by formula (V) (11.10 g, 0.035 mol) was dissolved in methanol (200 mL) at room temperature under a nitrogen atmosphere, and compound 2,6-diisopropylaniline (42 mL, 0.21 mol) and formic acid (0.2 mL, 0.005 mol) were added. The mixture was stirred at 80 ℃ under reflux for 4 h, and then 2,6-diisopropylaniline and methanol were removed by distillation under reduced pressure. The resulting product was precipitated by ethanol, washed, and recrystallized from dichloromethane / petroleum ether to obtain the compound represented by formula (III) III-3 in a yield of 52.2%; 1 H NMR (400 MHz, CDCl3): δ 1.15 (t, 24H), 2.34 (s, 6H), 2.80 (t, 4H), 7.08-7.10 (m, 2H), 7.12-7.18 (m, 4H), 7.62 (t, 1H), 7.90-7.94 (m, 4H), 7.98 (d, 2H), 8.18 (d, 2H), 9.00 (s, 1H);

[0413] The compound represented by formula (II) II-5 has the following two preparation methods:

[0414] Compound III-3 shown in formula (III) III-3 (3.2 g, 5 mmol) was dissolved in tetrahydrofuran (500 mL) at room temperature under anaerobic condition, 1M trimethylaluminum (25 mL, 25 mmol) was added dropwise at -78 °C, after the addition was completed, the temperature was raised to room temperature and stirred for 3 h, then ammonium chloride aqueous solution was added to terminate the reaction, then the organic phase was extracted with ethyl acetate, and the organic phase was separated by silica gel gel chromatography to obtain compound II-5 shown in formula (II), the yield was 64.2%; LCMS: [M+H] + = 667.4; 1 H NMR (600 MHz, CDCl3) δ 8.76 (s, 1H), 8.20 (dd, 2H), 7.76-7.71 (m, 4H), 7.59 (t, J = 6.6 Hz, 1H), 7.50 (dd, 2H), 7.07 (s, 6H), 4.53 (s, 2H), 3.36-3.33 (m, 4H), 1.52 (s, 12H), 1.08 (d, J = 6.0 Hz, 24H);

[0415] Compound III-3 shown in formula (III) III-3 (3.2 g, 5 mmol) was dissolved in tetrahydrofuran (500 mL) at room temperature under anaerobic condition, 1M trimethylaluminum (25 mL, 25 mmol) was added dropwise at -78 °C, after the addition was completed, the temperature was raised to room temperature and stirred for 3 h, then ammonium chloride aqueous solution was added to terminate the reaction, then the organic phase was extracted with ethyl acetate, and the organic phase was separated by silica gel gel chromatography to obtain compound II-5 shown in formula (II), the yield was 64.2%; LCMS: [M+H] + = 667.4;

[0416] In the glove box, 2.67 g of compound II-5 shown in formula (II) II-5 (4.13 mmol) was dissolved in 20 mL of dry toluene, 3.4 mL of n-butyllithium in hexane (8.5 mmol) was added dropwise, after reaction at 20 °C for 1.5 h, 2.7 g (8.5 mmol) of hafnium tetrachloride was added, and the temperature was raised to 120 °C and refluxed for 2 h; 9.4 mL of methyl magnesium bromide (28.2 mmol) was added, stirred at 25 °C for 12 h, the toluene was removed, 15 mL of dry n-hexane was added, stirred for 15 min, then filtered and washed with dry n-hexane, the filtrate was removed, 15 mL of dry toluene was added, the filtrate was collected by filtration, and the solvent was removed to obtain a yellow solid, which was complex 160, the yield was 60.1%; elemental analysis test C 50 H 66 Hf2N4: Theoretical calculation value: C, 55.60; H, 6.16; N, 5.19; Test value: C, 55.41; H, 6.32, N, 5.22;

[0417] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.2 mg (2 μmol) of complex 160 were added, the reaction was carried out at 60°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60°C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0418] Example 27

[0419] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.2 mg (2 μmol) of complex 160 were added, the reaction was carried out at 60°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60°C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0420] Example 28

[0421] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.2 mg (2 μmol) of complex 160 were added, the reaction was carried out at 60°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60°C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0422] Example 29

[0423] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 400 mL of dried decane was injected into the reactor, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.2 mg (2 μmol) of complex 160 were added, the reaction was carried out at 100°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60°C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0424] Example 30

[0425] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130°C for 3 h, vacuumed while hot and replaced with N2for 3 times, 400 mL of dried decane was injected into the reactor, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.2 mg (2 μmol) of complex 160 were added, the reaction was carried out at 100°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60°C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0426] Example 31

[0427] A 50 mL Schlenk reactor was dried by vacuum for 2 h and replaced with N2for 3 times, 5 mL of dried toluene solution was added, 5 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.2 mg (2 μmol) of complex 160 were added, the reaction was carried out at 40°C with vigorous stirring for 60 min, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum drying oven at 60°C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0428] Example 32

[0429] Complex 153: a complex of formula (I) wherein R1and R2are methyl, R3and R7are isopropyl, R4to R6are H, M is Hf, X is Cl, and n is 2;

[0430] In a glove box, 0.667 g of compound of formula (II) II-5 (1.00 mmol) was dissolved in 20 mL of dry toluene, 0.8 mL of n-butyllithium in hexane (2.0 mmol) was added dropwise, after 1.5 h of reaction at 20 °C, 0.64 g (2.0 mmol) of hafnium tetrachloride was added, and the temperature was raised to 120 °C for 2 h of reflux; filtration, drying under vacuum, and washing with dry n-hexane gave a yellow solid, which was complex 153, with a yield of 63.2%; elemental analysis test: C 46 H 54 Cl4Hf2N4; the theoretical calculation values were C, 47.56; H, 4.69; N, 4.82; the test values were C, 47.41; H, 4.72, N, 5.02;

[0431] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dry decane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L in toluene), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol), and 2.3 mg of complex 153 (2 μmol) were added, the reaction was carried out at 100 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution, and polymerization activity of the obtained polymer are shown in Table 1.

[0432] Example 33

[0433] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dry decane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L in toluene), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol), and 2.3 mg of complex 153 (2 μmol) were added, the reaction was carried out at 100 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60 °C, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution, and polymerization activity of the obtained polymer are shown in Table 1.

[0434] Example 34

[0435] Complex 163: a complex represented by formula (I), wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2;

[0436] The compound represented by formula (V) (9.5 g, 0.030 mol) was dissolved in methanol (200 mL) at room temperature under a nitrogen atmosphere, compound 2,4,6-trimethylaniline (28.5 mL, 0.20 mol) and formic acid (0.2 mL, 0.005 mol) were added, the temperature was raised to 80°C and refluxed for 4 h, 2,4,6-trimethylaniline and methanol were removed by distillation under reduced pressure, then precipitated with ethanol, washed, recrystallized with dichloromethane / petroleum ether to obtain the compound represented by formula (III) III-4, with a yield of 63.8%; LCMS: [M+H] + = 552.5;

[0437] The compound represented by formula (III) III-4 (2.75 g, 5 mmol) was dissolved in tetrahydrofuran (500 mL) at room temperature under anaerobic conditions, 1M trimethylaluminum (25 mL, 25 mmol) was added dropwise at -78°C, after the addition was completed, the temperature was raised to room temperature and stirred for 3 h, then ammonium chloride aqueous solution was added to terminate the reaction, then the organic phase was extracted with ethyl acetate, and the organic phase was separated by silica gel gel chromatography to obtain the compound represented by formula (II) II-6, with a yield of 66.3%; LCMS: [M+H] + = 583.2;

[0438] In the glove box, 2.33 g of the compound represented by formula (II) II-6 (4.0 mmol) was dissolved in 20 mL of dry toluene, 3.2 mL of n-butyllithium in hexane (8.0 mmol) was added dropwise, after reaction at 20°C for 1.5 h, 2.55 g (8.0 mmol) of hafnium tetrachloride was added, the temperature was raised to 120°C and refluxed for 2 h; 9.4 mL (28.2 mmol) of methylmagnesium bromide was added, stirred at 25°C for 12 h, the toluene was removed, 15 mL of dry n-hexane was added, stirred for 15 min, then allowed to stand, filtered and washed with dry n-hexane, the filtrate was removed, 15 mL of dry toluene was added, the filtrate was collected by filtration, and the solvent was removed to obtain a yellow solid, which was complex 163, with a yield of 62.5%; elemental analysis test: C 44 H 54 Hf2N4; the theoretical calculation value is: C, 53.06; H, 5.47; N, 5.63; the test value is: C, 53.21; H, 5.71, N, 5.72;

[0439] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the reactor, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.0 mg of complex 163 were added, the reactor was kept at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0440] Example 35

[0441] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times, 500 mL of dried hexane was injected into the reactor, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.0 mg of complex 163 were added, the reactor was kept at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was released, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight, and sample analysis was performed, the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0442] Example 36

[0443] Complex 202: a complex represented by formula (I), wherein R1and R2are methyl, R3and R7are isopropyl, R4-R6are H, M is Zr, X is methyl, and n is 2;

[0444] In a glove box, 2.00 g of a compound represented by formula (II) II-5 (3 mmol) was dissolved in 10 mL of dry toluene, 2.6 mL of n-butyllithium hexane solution (6.5 mmol) was slowly added dropwise, after reaction at 20 °C for 1.5 h, 1.40 g (6.0 mmol) of zirconium tetrachloride was added, and the temperature was increased to 120 °C for reflux for 2 h; 6.0 mL of methyl magnesium bromide (18 mmol) was added, and stirred at 25 °C for 12 h, the toluene was removed by suction, 20 mL of dry n-hexane was added, stirred for 15 min, and then placed, filtered and washed with dry n-hexane, the filtrate was removed by suction, 30 mL of dry toluene was added again, the filtrate was collected by filtration, and the solvent was removed after suction to obtain a brown-green solid, which was complex 202, with a yield of 67.8%; elemental analysis test: C50 H 66 N4Zr2; Calcd: C, 66.32; H, 7.35; N, 6.19; Found: C, 66.21; H, 7.61, N, 6.22;

[0445] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. The reactor was charged with 500 mL of dried decane, 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L in toluene), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 1.8 mg of complex 202 (2 μmol). The reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min. The ethylene was then released and the reaction mixture was neutralized with 10 wt% hydrochloric acid in ethanol solution. The precipitated solid was collected and dried to constant weight in a vacuum oven at 60 °C. The resulting polymer was analyzed and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity are shown in Table 1.

[0446] Comparative Example 1

[0447] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot and replaced with N2for 3 times. The reactor was charged with 500 mL of dried decane, 20 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L in toluene), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 1.8 mg of complex 202 (2 μmol). The reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min. The ethylene was then released and the reaction mixture was neutralized with 10 wt% hydrochloric acid in ethanol solution. The precipitated solid was collected and dried to constant weight in a vacuum oven at 60 °C. The resulting polymer was analyzed and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity are shown in Table 1.

[0448] Comparative Example 2

[0449] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was dried at 130 °C for 3 h, vacuumed while hot and purged with N2for 3 times. 500 mL of dried hexane was injected into the reactor, followed by 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.2 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (4 μmol) and 2.5 mg of complex A (4 μmol). The reaction was carried out at 60 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, and then the ethylene was released. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight. The obtained polymer was analyzed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the polymer are shown in Table 1.

[0450] Comparative Example 3

[0451] A 50 mL Schlenk reactor was dried by vacuuming for 2 h and purging with N2for 3 times. 5 mL of dried toluene was injected into the reactor, followed by 5 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylmethyl tetrakis(pentafluorophenyl)borate (4 μmol) and 2.5 mg of complex A (4 μmol). The reaction was carried out at 40 °C with vigorous stirring for 60 min. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight. The obtained polymer was analyzed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the polymer are shown in Table 1.

[0452] Comparative Example 4

[0453] A 1 L stainless steel polymerization reactor equipped with mechanical stirring was dried at 130 °C for 3 h, vacuumed while hot and purged with N2for 3 times. 500 mL of dried decane was injected into the reactor, followed by 20 mL of 1-octene, 2.0 mL of methylaluminoxane (10 wt% toluene solution) and 2.7 mg of complex B (reference: Angew. Chem. Int. Ed. 2006, 45, 3278-3283) (4 μmol). The reaction was carried out at 120 °C under 10 atm of ethylene pressure with vigorous stirring for 30 min, and then the ethylene was released. The reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, and the precipitated solid was collected and dried in a vacuum oven at 60 °C to constant weight. The obtained polymer was analyzed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the polymer are shown in Table 1.

[0454] Comparative Example 5

[0455] 50 mL Schlenk flask was dried under vacuum for 2 h and purged with N2three times, 5 mL of dry toluene was added, 5 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol), and 2.7 mg (4 μmol) of complex B (reference: Angew. Chem. Int. Ed. 2006, 45, 3278-3283) were added, and the reaction was stirred vigorously at 60 °C for 60 min. The reaction solution was neutralized with 10 wt% hydrochloric acid-acidified ethanol solution, the precipitated solid was collected, dried in a vacuum oven at 60 °C to constant weight, and weighed, and sample analysis was performed. The test data of the weight average molecular weight, molecular weight distribution, and polymerization activity of the obtained polymer are shown in Table 1.

[0456] Comparative Example 6

[0457] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot, and purged with N2three times, 500 mL of dried hexane was injected into the polymerization kettle, 1.0 mL of triisobutylaluminum (1 mol / L hexane solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol), and 2.7 mg (4 μmol) of complex B (reference: Angew. Chem. Int. Ed. 2006, 45, 3278-3283) were added, and the reaction was stirred vigorously at 60 °C for 30 min under 10 atm of ethylene pressure, and then the ethylene was released. The reaction solution was neutralized with 10 wt% hydrochloric acid-acidified ethanol solution, the precipitated solid was collected, dried in a vacuum oven at 60 °C to constant weight, and weighed, and sample analysis was performed. The test data of the weight average molecular weight, molecular weight distribution, and polymerization activity of the obtained polymer are shown in Table 1.

[0458] Comparative Example 7

[0459] A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 3 h, vacuumed while hot, and purged with N2three times, 300 mL of dried decane was injected into the polymerization kettle, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol), and 2.9 mg (4 μmol) of complex C (reference: Organometallics 2011, 30, 3318) were added, and the reaction was stirred vigorously at 140 °C for 30 min under 12 atm of ethylene pressure, and then the ethylene was released. The reaction solution was neutralized with 10 wt% hydrochloric acid-acidified ethanol solution, the precipitated solid was collected, dried in a vacuum oven at 60 °C to constant weight, and weighed, and sample analysis was performed. The test data of the weight average molecular weight, molecular weight distribution, and polymerization activity of the obtained polymer are shown in Table 1.

[0460] Comparative Example 8

[0461] A 1L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 3h, vacuumed while hot and replaced with N2for 3 times, 300 mL of dried decane was injected into the polymerization kettle, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.6 mg (2 μmol) of complex D (reference: ACS Catal. 2015, 5, 5272-5282) were added, the reaction was carried out at 140°C under 12 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60°C, and sample analysis was performed. The test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0462] Comparative Example 9

[0463] A 1L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 3h, vacuumed while hot and replaced with N2for 3 times, 300 mL of dried decane was injected into the polymerization kettle, 100 mL of 1-octene, 1.0 mL of triisobutylaluminum (1 mol / L toluene solution), 3.7 mg of triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (4 μmol) of complex E (synthesis reference: ACS Catal., 2017, 7, 6930) were added, the reaction was carried out at 140°C under 10 atm of ethylene pressure with vigorous stirring for 30 min, then the ethylene was vented, the reaction solution was neutralized with 10 wt% hydrochloric acid acidified ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum drying oven at 60°C, and sample analysis was performed. The test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0464] Comparative Example 10

[0465] 50 mL Schlenk tube was vacuum dried for 2 h and replaced with N2 for 3 times, 5 mL dry toluene solution was added, 5 mL 1-octene, 1.0 mL triisobutylaluminum (1 mol / L toluene solution), 3.7 mg triphenylphosphonium tetra(pentafluorophenyl)borate (4 μmol) and 2.3 mg (4 μmol) complex E were added, the reaction was stirred vigorously at 40 °C for 60 min, the reaction solution was neutralized with 10 wt% hydrochloric acid in ethanol solution, the precipitated solid was collected and dried to constant weight in a vacuum oven at 60 °C, and sample analysis was performed, and the test data of the weight average molecular weight, molecular weight distribution and polymerization activity of the obtained polymer are shown in Table 1.

[0466] Table 1

[0467] As can be seen from the results in Table 1, the pyridine amine group IVB group binuclear metal organic complex described in the application is applied to olefin polymerization, under similar polymerization conditions, has higher polymerization activity, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained in the comparative example, and the molecular weight distribution of the obtained polymer is wide.

[0468] Test example

[0469] The molecular weight distribution of the polymers prepared in Examples 12-13 and Comparative Example 8 was characterized by GPC spectrum, and the results are shown in Figure 1;

[0470] As can be seen from Figure 1, the pyridine amine group IVB group binuclear metal organic complex described in the application is applied to olefin polymerization, the molecular weight distribution of the polymer prepared therefrom presents a clear bimodal structure, while the complex D described in Comparative Example 8 is applied to olefin polymerization, the molecular weight distribution of the polymer prepared therefrom presents a clear unimodal structure.

[0471] The above describes the preferred embodiments of the application in detail, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application, and all fall within the protection scope of the application.

Claims

A pyridinamine-based group IVB binuclear metal organic complex characterized in that, The structural formula of the pyridine amine group ⅣB binuclear metal organic complex is shown as formula (I), R1and R2are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C30alkyl, C1-C30alkoxy, substituted or unsubstituted C3-C30cycloalkyl, C3-C30cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C40aryloxy; R3-R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C1-C30alkoxy, substituted or unsubstituted C2-C30dialkylamino, substituted or unsubstituted C3-C30cycloalkoxy, substituted or unsubstituted C4-C30dicycloalkylamino, substituted or unsubstituted C6-C40aryl, substituted or unsubstituted C7-C40aryloxy, substituted or unsubstituted C6-C40arylamino, and substituted or unsubstituted C3-C40trihydrocarbylsilyl, or any two or more of R3-R7are connected to form a ring structure; X is selected from the group consisting of a divalent substituent having 1-40 atoms, halogen, or C1-C20hydrocarbyl; n is 1 or 2; M is selected from Group IVB metals. The Group IVB dinuclear metal organic complex of pyridinamine according to claim 1, characterized in that, R1and R2are each independently selected from the group consisting of hydrogen, C1-C20alkyl, C1-C20alkoxy, C3-C20cycloalkyl, C3-C20cycloalkoxy, substituted or unsubstituted C6-C30aryl, and C6-C30aryloxy; Preferably, R3-R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C20alkyl, C1-C20alkoxy, C2-C20dialkylamino, substituted or unsubstituted C3-C20cycloalkyl, C3-C20cycloalkoxy, C4-C20dicycloalkylamino, substituted or unsubstituted C6-C30aryl, C7-C30aryloxy, C6-C30arylamino, and C3-C30trihydrocarbylsilyl, or any two or more of R3-R7are connected to form a ring structure; Preferably, when n is 1, X is a divalent substituent having 1-40 atoms, and when n is 2, X is halogen or C1-C20hydrocarbyl. Preferably, M is selected from titanium, zirconium, or hafnium. The Group IVB dinuclear metal organic complex of pyridinamine according to claim 1 or 2, characterized in that, R1and R2are each independently selected from the group consisting of hydrogen, C1-C6alkyl, phenyl, substituted C7-C20phenyl, naphthyl, substituted C7-C20naphthyl, anthryl, indenyl, fluorenyl, phenoxy, substituted C7-C20phenoxy, or substituted C7-C20naphthoxy; Preferably, R3-R7are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C3-C20cycloalkyl, and substituted or unsubstituted C6-C30aryl, or any two or more of R3-R7are connected to form a ring structure; Preferably, when n is 1, X is selected from the group consisting of an alkylene having 1-20 atoms, an arylene having 1-20 atoms, a diaminide having 1-20 atoms, or a diene having 1-20 atoms, and when n is 2, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10alkyl, and substituted or unsubstituted C6-C10aryl. The pyridinamine group IVB double nuclear metal organic complex according to any one of claims 1-3, characterized in that, The pyridine amine-based Group IVB dinuclear metal organic complex is selected from the group consisting of: Complex 1: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is Cl, n is 2; Complex 2: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are ethyl, R4-R6 are H, M is Hf, X is Cl, n is 2; Complex 3: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are methyl, R4-R6 are H, M is Hf, X is Cl, n is 2; Complex 4: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3, R5 and R7 are methyl, R4 and R6 are H, M is Hf, X is Cl, n is 2; Complex 5: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are phenyl, R4-R6 are H, M is Hf, X is Cl, n is 2; Complex 6: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are cyclohexyl, R4-R6 are H, M is Hf, X is Cl, n is 2; Complex 7: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Hf, X is Cl, n is 2; Complex 8: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is methyl, n is 2; Complex 9: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are ethyl, R4-R6 are H, M is Hf, X is methyl, n is 2; Complex 10: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are methyl, R4-R6 are H, M is Hf, X is methyl, n is 2; Complex 11: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3, R5 and R7 are methyl, R4 and R6 are H, M is Hf, X is methyl, n is 2; Complex 12: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are phenyl, R4-R6 are H, M is Hf, X is methyl, n is 2; Complex 13: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are cyclohexyl, R4-R6 are H, M is Hf, X is methyl, n is 2; Complex 14: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Hf, X is methyl, n is 2; Complex 15: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is benzyl, n is 2; Complex 16: a complex of formula (I) wherein R1 is phenyl, R2 is hydrogen, R3 and R7 are ethyl, R4-R6 are H, M is Hf, X is benzyl, n is 2; Complex 17: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 18: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2; Complex 19: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 20: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 21: a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 22: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 23: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 24: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 25: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2; Complex 26: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 27: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 28: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 29: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 30: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 31: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 32: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2; Complex 33: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Hf, X is methyl, and n is 2; Complex 34: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is methyl, and n is 2; Complex 35: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is methyl, and n is 2; Complex 36: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are isopropyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 37: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are ethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 38: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are methyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 39: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2; Complex 40: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are phenyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 41: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 42: a complex of formula (I) wherein R1is 2-methylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 43: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 44: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 45: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 46: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2; Complex 47: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 48: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 49: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 50: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 51: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 52: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 53: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2; Complex 54: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 55: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 56: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 57: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 58: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 59: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 60: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2; Complex 61: a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 62 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is benzyl, and n is 2. Complex 63 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2. Complex 64 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 65 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 66 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 67 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2. Complex 68 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 69 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 70 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 71 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is methyl, and n is 2. Complex 72 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2. Complex 73 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2. Complex 74 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2. Complex 75 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2. Complex 76 is a complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2. Complex 77: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 78: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 79: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 80: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 81: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2; Complex 82: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 83: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 84: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is benzyl, and n is 2; Complex 85: A complex of formula (I) wherein R1, R3and R7are isopropyl, R2is hydrogen, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 86: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 87: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 88: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2; Complex 89: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 90: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 91: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is Cl, and n is 2; Complex 92: A complex of formula (I) wherein R1, R3and R7are isopropyl, R2is hydrogen, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 93: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 94: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 95: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2; Complex 96: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 97: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 98: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Hf, X is methyl, and n is 2; Complex 99: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 100: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 101: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 102: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is Cl, and n is 2; Complex 103: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 104: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 105: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 106: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 107: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 108: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 109: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2; Complex 110: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 111: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 112: A complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 113: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 114: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 115: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 116: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is Cl, and n is 2; Complex 117: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 118: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 119: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is Cl, and n is 2; Complex 120: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 121: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 122: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 123: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2; Complex 124: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 125: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 126: A complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 127: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 128: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 129: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 130: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2; Complex 131: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 132: A complex of formula (I) wherein R1is t-butyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 133: A complex of formula (I) wherein R1, R3and R7are isopropyl, R2is hydrogen, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 134: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 135: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 136: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Zr, X is methyl, and n is 2; Complex 137: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 138: A complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Zr, X is methyl, and n is 2; Complex 139 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Zr, X is methyl, and n is 2. Complex 140 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 141 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 142 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 143 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Ti, X is methyl, and n is 2. Complex 144 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 145 is a complex of formula (I) wherein R1is phenyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 146 is a complex of formula (I) wherein R1is 2-isopropylphenyl, R2is hydrogen, R3and R7are trifluoromethyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 147 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are isopropyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 148 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are ethyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 149 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are methyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 150 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3, R5and R7are methyl, R4and R6are H, M is Ti, X is methyl, and n is 2. Complex 151 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are phenyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 152 is a complex of formula (I) wherein R1is isopropyl, R2is hydrogen, R3and R7are cyclohexyl, R4-R6are H, M is Ti, X is methyl, and n is 2. Complex 153 is a complex of formula (I) wherein R1and R2are methyl, R3and R7are isopropyl, R4-R6are H, M is Hf, X is Cl, and n is 2. Complex 154 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are ethyl, R4~R6 are H, M is Hf, X is Cl, and n is 2. Complex 155 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are methyl, R4~R6 are H, M is Hf, X is Cl, and n is 2. Complex 156 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Hf, X is Cl, and n is 2. Complex 157 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are phenyl, R4~R6 are H, M is Hf, X is Cl, and n is 2. Complex 158 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are cyclohexyl, R4~R6 are H, M is Hf, X is Cl, and n is 2. Complex 159 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are trifluoromethyl, R4~R6 are H, M is Hf, X is Cl, and n is 2. Complex 160 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are isopropyl, R4~R6 are H, M is Hf, X is methyl, and n is 2. Complex 161 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are ethyl, R4~R6 are H, M is Hf, X is methyl, and n is 2. Complex 162 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are methyl, R4~R6 are H, M is Hf, X is methyl, and n is 2. Complex 163 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Hf, X is methyl, and n is 2. Complex 164 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are phenyl, R4~R6 are H, M is Hf, X is methyl, and n is 2. Complex 165 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are cyclohexyl, R4~R6 are H, M is Hf, X is methyl, and n is 2. Complex 166 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are trifluoromethyl, R4~R6 are H, M is Hf, X is methyl, and n is 2. Complex 167 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are isopropyl, R4~R6 are H, M is Hf, X is benzyl, and n is 2. Complex 168 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are ethyl, R4~R6 are H, M is Hf, X is benzyl, and n is 2. Complex 169 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are methyl, R4~R6 are H, M is Hf, X is benzyl, and n is 2. Complex 170: a complex of formula (I), wherein R1and R2are methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is benzyl, and n is 2; Complex 171: a complex of formula (I), wherein R1and R2are methyl, R3and R7are phenyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 172: a complex of formula (I), wherein R1and R2are methyl, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 173: a complex of formula (I), wherein R1and R2are methyl, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is benzyl, and n is 2; Complex 174: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are isopropyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 175: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are ethyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 176: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are methyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 177: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is Cl, and n is 2; Complex 178: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are phenyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 179: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are cyclohexyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 180: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are trifluoromethyl, R4to R6are H, M is Hf, X is Cl, and n is 2; Complex 181: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are isopropyl, R4to R6are H, M is Hf, X is methyl, and n is 2; Complex 182: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are ethyl, R4to R6are H, M is Hf, X is methyl, and n is 2; Complex 183: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3and R7are methyl, R4to R6are H, M is Hf, X is methyl, and n is 2; Complex 184: a complex of formula (I), wherein R1is phenyl, R2is methyl, R3, R5and R7are methyl, R4and R6are H, M is Hf, X is methyl, and n is 2; Complex 185 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are phenyl, R4-R6 are H, M is Hf, X is methyl, and n is 2. Complex 186 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Hf, X is methyl, and n is 2. Complex 187 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Hf, X is methyl, and n is 2. Complex 188 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Hf, X is benzyl, and n is 2. Complex 189 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are ethyl, R4-R6 are H, M is Hf, X is benzyl, and n is 2. Complex 190 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are methyl, R4-R6 are H, M is Hf, X is benzyl, and n is 2. Complex 191 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Hf, X is benzyl, and n is 2. Complex 192 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are phenyl, R4-R6 are H, M is Hf, X is benzyl, and n is 2. Complex 193 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Hf, X is benzyl, and n is 2. Complex 194 is a complex shown by the formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Hf, X is benzyl, and n is 2. Complex 195 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Zr, X is Cl, and n is 2. Complex 196 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are ethyl, R4-R6 are H, M is Zr, X is Cl, and n is 2. Complex 197 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are methyl, R4-R6 are H, M is Zr, X is Cl, and n is 2. Complex 198 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Zr, X is Cl, and n is 2. Complex 199 is a complex shown by the formula (I), wherein R1 and R2 are methyl, R3 and R7 are phenyl, R4-R6 are H, M is Zr, X is Cl, and n is 2. Complex 200: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 201: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 202: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 203: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are ethyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 204: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are methyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 205: a complex represented by formula (I), wherein R1 and R2 are methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Zr, X is methyl, and n is 2; Complex 206: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are phenyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 207: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 208: a complex represented by formula (I), wherein R1 and R2 are methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 209: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 210: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are ethyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 211: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are methyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 212: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Zr, X is Cl, and n is 2; Complex 213: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are phenyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 214: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 215: a complex represented by formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Zr, X is Cl, and n is 2; Complex 216: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are isopropyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 217: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are ethyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 218: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are methyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 219: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3, R5 and R7 are methyl, R4 and R6 are H, M is Zr, X is methyl, and n is 2; Complex 220: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are phenyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 221: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 222: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are trifluoromethyl, R4-R6 are H, M is Zr, X is methyl, and n is 2; Complex 223: a complex of formula (I), wherein R1 and R2 are methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Ti, X is methyl, and n is 2; Complex 224: a complex of formula (I), wherein R1 is phenyl, R2 is methyl, R3 and R7 are cyclohexyl, R4-R6 are H, M is Ti, X is methyl, and n is 2. A method for producing the pyridinamine-based group IVB dinuclear metal organic complex according to any one of claims 1 to 4, characterized in that The method comprises: The compound of formula (II) is reacted with a dehydrogenating agent in the presence of an organic solvent, followed by a second reaction with a M salt, and then optionally a reaction with a Grignard reagent; wherein the M salt is a halide of a Group IVB metal and / or a hydrocarbon compound of a Group IVB metal; R1-R7 are the same as defined in claim 1. The method according to claim 5, characterized in that The conditions of the first reaction include a temperature of -78-35°C and a time of 1-24h; Preferably, the molar ratio of the compound of formula (II) to the hydrogen abstractor is 1:2-5, preferably 1:2-4.6; Preferably, the hydrogen abstractor is selected from one or more of sodium hydride, potassium hydride, lithium hydride, tetramethylethylenediamine, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, lithium diisopropylamide, and C1-C6 alkyl lithium. The method according to claim 5 or 6, characterized in that The conditions of the second reaction include a temperature of 60-120°C and a time of 1-30h; Preferably, the molar ratio of the compound of formula (II) to the metal M in the M salt is 1:2-3, preferably 1:2-2.6; Preferably, the organic solvent is selected from one or more of tetrahydrofuran, diethyl ether, pentane, cyclopentane, n-hexane, cyclohexane, heptane, methylcyclohexane, toluene, xylene, chlorobenzene, and o-dichlorobenzene. The method according to any one of claims 5-7, characterized in that The method for preparing the compound of formula (II) comprises the following steps: (1) a third reaction of a compound represented by formula (V) and a compound represented by formula (IV) in the presence of a first solvent and formic acid and / or acetic acid, to obtain a compound represented by formula (III); (2) in the presence of a second solvent, subjecting the compound represented by formula (III) and Compound A to a fourth reaction; wherein the compound A is LiR1 and / or Al(R1)3; R1-R7 are the same as defined in claim 1. The method of claim 8, wherein In step (1), the third reaction is carried out at a temperature of 50-120°C for 4-24 hours. Preferably, in step (1), the molar ratio of the compound represented by formula (V) to the compound represented by formula (IV) is 1:2-8. Preferably, in step (1), the first solvent is selected from one or more of methanol, ethanol, toluene, xylene, benzene, diethyl ether and tetrahydrofuran. The method according to claim 8 or 9, characterized in that In step (2), the fourth reaction is carried out at a temperature of -78-120°C for 0.5-24 hours. Preferably, in step (2), the molar ratio of the compound represented by formula (III) to the compound A is 1:2-10. Preferably, in step (2), the second solvent is selected from one or more of methanol, ethanol, toluene, xylene, benzene, diethyl ether and tetrahydrofuran. A catalyst for the polymerization of olefins, characterized in that, The catalyst for olefin polymerization comprises a main catalyst and a cocatalyst, wherein the main catalyst is the pyridine amine-based group IVB binuclear metal organic complex according to any one of claims 1-4. Preferably, the cocatalyst is selected from one or more of aluminoxane, alkyl aluminum compound, chlorinated alkyl aluminum, alkyl zinc and optional organic boron compound. The catalyst for the polymerization of olefins according to claim 11, characterized in that, The aluminoxane is methyl aluminoxane and / or modified methyl aluminoxane. Preferably, the alkyl aluminum compound is selected from one or more of triethyl aluminum, triisobutyl aluminum and trioctyl aluminum. Preferably, the chlorinated alkyl aluminum is selected from one or more of monochloroethyl aluminum, sesquiethyl aluminum chloride and dichloroethyl aluminum. Preferably, the organic boron compound is selected from one or more of triphenylmethyl tetraphenylborate, triphenylmethyl tetraphenylborate, tris(pentafluorophenyl)boron, N,N-dimethylaniline tetraphenylborate, dioctadecylmethyl tertiary amine tetraphenylborate and dihydrogenated tallowmethyl tertiary amine tetraphenylborate. The catalyst for the polymerization of olefins according to claim 11 or 12, characterized in that, The molar ratio of aluminum in the cocatalyst to metal M in the main catalyst is 1-10000:1, and the molar ratio of boron in the cocatalyst to metal M in the main catalyst is 0-10:

1. A process for the polymerization of olefins, characterized in that, The olefin polymerization reaction is carried out in the presence of the catalyst for olefin polymerization according to any one of claims 11-13. Preferably, the polymerization reaction is carried out at a temperature of -78-250°C, more preferably -20-200°C, and at a pressure of 0.1-100 atm, more preferably 0.1-50 atm.

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