Metallocene complex and production method, catalyst composition and olefin polymerization method, and olefin polymer

Abstract

The present invention provides a metallocene complex and a method for producing the same, a catalyst composition, an olefin polymerization method, and an olefin polymer. The metallocene complex has a structure represented by formula I. The catalyst composition containing the metallocene complex of the present invention exhibits improved catalytic activity, has a high ability to control the structural regularity of the conjugated diolefin structural unit, and has a high ability to copolymerize ethylene with a conjugated diolefin. In addition, the metallocene complex of the present invention has a simple production process and low cost. [Formula 1] JPEG2025515221000023.jpg86169

Description

Detailed Description of the Invention

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of Chinese Patent Application No. 202210586608.1, filed on May 27, 2022, the contents of which are incorporated herein by reference.

[0002] [Technical field] The present invention relates to a metallocene complex and a method for producing the same. The present invention also relates to a catalyst composition containing the metallocene complex. The present invention further relates to an olefin polymerization process using the catalyst composition and an olefin polymer produced by the process.

[0003] [Background technology] Metallocene complexes are compounds in which one or more cyclopentadienyls or their derivatives are coordinated to a central metal, and they play a very important role as catalysts in various polymerization reactions. Due to the different types of ligands and central metals, metallocene complexes exhibit different catalytic properties in polymerization reactions.

[0004] Numerous polymerization catalysts have been proposed for the polymerization of conjugated diolefins. For example, it is known that high-cis 1,4-conjugated diene polymers can be obtained by using a composite catalyst system primarily composed of a neodymium compound and an organoaluminum compound. Some of these polymers are industrially used as catalyst systems for butadiene polymerization. However, there has been a demand for an efficient method for producing conjugated diene polymers with a high content of cis 1,4 structures in the microstructure, high molecular weight, and narrow molecular weight distribution. Therefore, it is necessary to develop a polymerization catalyst.

[0005] Ethylene, a widely used and readily available monomer, is widely used in the plastics industry. Conjugated dienes, especially butadiene and isoprene, are the most important monomers for synthetic rubber. Butadiene, a by-product of the petroleum route used to produce ethylene, was once traded at a price close to that of ethylene. Changes in ethylene production routes have led to a decrease in butadiene production and a significant increase in its price. Meanwhile, the price of ethylene has declined. Therefore, the use of ethylene as a raw material for tire rubber production is highly anticipated and could significantly reduce raw material costs. However, conjugated dienes and α-olefins are difficult to copolymerize due to their different polymerization mechanisms. Therefore, catalyzing the copolymerization of ethylene and conjugated dienes using the same catalyst system has been a challenge, and both academia and industry have been working hard to achieve this. There is great promise for the development of metallocene complexes with higher catalytic activity, greater control over the structural regularity of conjugated diolefin structural units, and greater copolymerization ability between ethylene and conjugated diolefins.

[0006] In 2015, Michiue et al. reported the production of ethylene / propylene and butadiene copolymers using a series of silicon-bridged disubstituted indenyl zirconium catalysts in the presence of hydrogen (K. Michiue, M. Mitani, T. Fujita, Catalysts 2015, 5, 2001-2017). The catalyst activity was high, resulting in higher molecular weight polymers. As the steric hindrance of the indene substituents increased, the vinyl content in the copolymer increased. However, the resulting copolymers had a low butadiene insertion rate, and the copolymers contained cyclopropyl and cyclopentyl moieties. Because rare earth catalysts have a good affinity for conjugated diolefins, attempts have also been made to copolymerize ethylene with conjugated diolefins. Boisson et al. reported a series of dicyclopentadienyl neodymium catalysts that can efficiently catalyze the copolymerization of ethylene and butadiene (M. Llauro, C. Monnet, F. Barbotin, V. Monteil, R. Spitz, C. Boisson, Macromolecules 2001, 34, 6304-6311; H. Nsiri, I. Belaid, P. Larini, J. Thuilliez, C. Boisson, L. Perrin, ACS Catal. 2016, 6, 1028-1036). The butadiene content in the copolymer was relatively high, and it was present mainly in the trans 1,4-structure. The molecular weight of the polymer was insufficient, and the polymer contained cyclohexyl units.

[0007] Transition metal compounds with heterocyclic fused five-membered ring π-ligands and their use as catalysts for the polymerization of monoolefins have been reported, with the advantages of high activity and high molecular weight. However, there have been few reports on catalysts for ethylene-conjugated diolefin copolymerization. There have been no reports on dimetallocene rare earth metals with heterocyclic fused rings and their use in ethylene-conjugated diolefin copolymerization.

[0008] [Summary of the Invention] [Problem to be solved by the invention] The object of the present invention is to provide a catalyst composition which has improved catalytic activity and can more precisely control the structure of conjugated diolefin structural units, thereby improving the structural regularity of the conjugated diolefin structural units in the produced polymer, and which, when used in the copolymerization of ethylene and conjugated diolefin, can effectively control the copolymer composition of the copolymer.

[0009] [Means for solving the problem] According to a first aspect of the present invention, there is provided a metallocene complex having the structure shown in Formula I: [ka] (In Formula I, Ln is a lanthanide, scandium, or yttrium; R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 are the same or different and each independently represent hydrogen, C1 to C 20 Alkyl, C6-C 30 aryl, or -SiR 23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different and each independently represent hydrogen or C1 to C 20 is an alkyl of R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represents hydrogen or C1-C5 alkyl, E is O, S, or NR 17 and R 17 is C1 to C5 alkyl or C6 to C 12 )

[0010] According to a second aspect of the present invention, there is provided a method for manufacturing a semiconductor device comprising: Step 1: contacting a precursor compound with a heterocyclic compound selected from the compounds of formula 2-2-1 and formula 2-2-2 in the presence of an organolithium; Step 2, contacting the mixture obtained in Step 1 with an amine represented by formula 2-3; The precursor compound is selected from compounds represented by formula 2-1: LnX (Formula 2-1) In Formula 2-1, Ln is a lanthanide, scandium, or yttrium; X is a halogen atom, preferably chlorine; [ka] In Formula 2-2-1 and Formula 2-2-2, R 201 , R 202 , R 203 , R 204 , and R 205 are the same or different and each independently represent hydrogen, C1 to C 20 Alkyl, C6-C 30 aryl, or -SiR 23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different and each independently represent hydrogen or C1 to C 20 is an alkyl of In Formula 2-2-1 and Formula 2-2-2, E is O, S, or NR 17 and R 17 is C1-C5 alkyl, C6-C 12 is an aryl of [ka] In Equation 2-3, R 206 , R 207 , R 208 , R 209 , R 210 , and R 211are the same or different and each independently represents hydrogen or C1-C5 alkyl, There is provided a method for preparing a metallocene complex according to the first aspect of the present invention, wherein M is an alkali metal atom, preferably potassium or sodium.

[0011] According to a third aspect of the present invention, there is provided a catalyst composition comprising a metallocene complex and a co-catalyst, wherein the metallocene complex is the metallocene complex according to the first aspect of the present invention.

[0012] According to a fourth aspect of the present invention, there is provided a process for polymerising olefins, comprising the step of contacting, under olefin polymerisation reaction conditions, at least one olefin with components in a catalyst composition, said catalyst composition being the catalyst composition described in the second aspect of the present invention.

[0013] According to a fifth aspect of the present invention, there is provided an olefin polymer produced by the method according to the fourth aspect of the present invention.

[0014] [Effects of the invention] The catalyst composition containing the metallocene complex of the present invention exhibits improved catalytic activity, has a high ability to control the structural regularity of the conjugated diolefin structural units, and has a high ability to copolymerize ethylene with conjugated diolefins. The catalyst composition containing the metallocene complex of the present invention can precisely control the structure of the conjugated diolefin structural units, thereby improving the structural regularity of the conjugated diolefin structural units in the produced polymer. The catalyst system containing the metallocene complex of the present invention has excellent copolymerizability, can efficiently achieve copolymerization of ethylene with conjugated diolefins, and can efficiently control the copolymer composition of the copolymer. The method for producing the metallocene complex of the present invention produces the metallocene complex by a "one-pot method," which efficiently simplifies the synthesis route, reduces operational complexity, and reduces operational costs.

[0015] [Mode for Carrying Out the Invention] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. With respect to numerical ranges, the endpoints of each range, the endpoints of each range and individual dot values, and the individual dot values ​​can be combined to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0016] According to a first aspect of the present invention, there is provided a metallocene complex having the structure shown in Formula I: [ka] (In Formula I, Ln is a lanthanide, scandium, or yttrium.)

[0017] In the present invention, the term "lanthanide" refers collectively to the 15 elements from lanthanum, numbered 57, to lutetium, numbered 71, on the periodic table.

[0018] In Formula I, specific examples of Ln may include, but are not limited to, scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), or lutetium (Lu).

[0019] Preferably, in formula I, Ln is gadolinium or scandium. More preferably, in formula I, Ln is gadolinium.

[0020] In Formula I, R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 are the same or different and each independently represent hydrogen, C1 to C 20Alkyl, C6-C 30 aryl, or -SiR 23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different and each independently represent hydrogen or C1 to C 20 and preferably R 23 , R 24 , and R 25 At least one of C1 to C 20 is an alkyl of.

[0021] In the present invention, C1 to C 20 The alkyl is C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl and C3-C 20 and specific examples may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, decyl and its various isomers, undecyl and its various isomers, dodecyl and its various isomers, tridecyl and its various isomers, tetradecyl and its various isomers, pentadecyl and its various isomers, cetyl and its various isomers, heptadecyl and its various isomers, octadecyl and its various isomers, nonadecyl and its various isomers, eicosyl and its various isomers, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0022] In the present invention, C6 to C 30Specific examples of aryl may include, but are not limited to, phenyl, tolyl, ethylphenyl, propylphenyl (wherein propyl may be n-propyl or isopropyl), butylphenyl (wherein butyl may be n-butyl, sec-butyl, isobutyl, or tert-butyl), naphthyl, anthracenyl, or phenanthrenyl.

[0023] In a preferred embodiment, in Formula I, R1 and R6 are each independently a C1-C5 alkyl, and R2, R4, R7, and R9 are each independently a C6-C 12 and R3, R5, R8, and R 10 are all hydrogen. In this preferred embodiment, R1 and R6 are preferably methyl, and R2, R4, R7, and R9 are preferably phenyl. In this preferred embodiment, Ln is preferably gadolinium.

[0024] In another preferred embodiment, in Formula I, R1, R4, R6, and R9 are each independently C1 to C 20 R2 and R7 are each independently an alkyl group of C6 to C 30 and R3, R5, R8, and R 10 In this preferred embodiment, R1, R4, R6, and R9 are each independently preferably C1 to C5 alkyl, and R2 and R7 are each independently preferably C6 to C8 alkyl. 12 and R is an aryl. More preferably, R, R, R, and R are methyl or isopropyl, and R and R are phenyl. Even more preferably, R and R are methyl, R and R are methyl or isopropyl, and R and R are phenyl. In this preferred embodiment, Ln is preferably gadolinium.

[0025] In yet another preferred embodiment, in Formula I, R1, R4, R6, and R9 are each independently C1 to C 20R2 and R7 are each independently an alkyl group of C6 to C 30 and R and R 10 are all hydrogen, and R3 and R8 are each independently -SiR 23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different, and each independently represents C1 to C 20 In this preferred embodiment, R1, R4, R6, and R9 are each independently preferably C1 to C5 alkyl, and R2 and R7 are each independently preferably C6 to C 12 R3 and R8 are each independently preferably -SiR 23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different and each independently represents hydrogen or C1-C5 alkyl, and R 23 , R 24 , and R 25 In this preferred embodiment, R1, R4, R6, and R9 are more preferably methyl, R2 and R7 are more preferably phenyl, and R3 and R8 are each independently more preferably -SiR 23 R 24 R 25 and R 23 , R 24 , and R 25 are all methyl. In this preferred embodiment, Ln is preferably gadolinium.

[0026] In Formula I, R 11 , R 12 , R 13 , R 14 , R 15 , and R 16are the same or different and each independently represent hydrogen or C1-C5 alkyl. Preferably, in formula I, R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represents hydrogen or C1-C5 alkyl, and R 11 , R 12 , and R 13 At least one of R is C1-C5 alkyl, 14 , R 15 , and R 16 At least one of R is C1-C5 alkyl. 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represents hydrogen or C1-C5 alkyl, and R 11 , R 12 , and R 13 At least two of R are C1-C5 alkyl; 14 , R 15 , and R 16 At least two of R are C1-C5 alkyl. 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represent a C1 to C5 alkyl. More preferably, in formula I, R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are all methyl.

[0027] In Formula I, E is O, S, or NR 17 and R 17is C1 to C5 alkyl or C6 to C 12 Preferably, in formula I, E is S.

[0028] According to the metallocene complex of the present invention, the metallocene complex is preferably a complex represented by formula II, formula III, formula IV or formula V. [ka]

[0029] According to the metallocene complex of the present invention, the metallocene complex is particularly preferably a complex represented by formula II, formula IV or formula V.

[0030] According to a second aspect of the present invention, there is provided a method for manufacturing a semiconductor device comprising: Step 1: contacting a precursor compound with a heterocyclic compound selected from the compounds of formula 2-2-1 and formula 2-2-2 in the presence of an organolithium; Step 2, contacting the mixture obtained in Step 1 with an amine represented by formula 2-3; The precursor compound is selected from compounds represented by formula 2-1: LnX (Formula 2-1) In Formula 2-1, Ln is a lanthanide, scandium, or yttrium, preferably gadolinium or scandium, more preferably gadolinium; X may be a halogen atom, for example fluorine, chlorine, bromine or iodine, but is preferably chlorine; [ka] In Formula 2-2-1 and Formula 2-2-2, R 201 , R 202 , R 203 , R 204 , and R 205 are the same or different and each independently represent hydrogen, C1 to C 20 Alkyl, C6-C 30 aryl, or -SiR23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different and each independently represent hydrogen or C1 to C 20 is an alkyl of In Formula 2-2-1 and Formula 2-2-2, E is O, S, or NR 17 and R 17 is C1-C5 alkyl, C6-C 12 aryl, preferably S; [ka] In Equation 2-3, R 206 , R 207 , R 208 , R 209 , R 210 , and R 211 are the same or different and each independently represents hydrogen or C1-C5 alkyl, The present invention provides a method for preparing a metallocene complex according to the first aspect, wherein M may be an alkali metal atom, for example, lithium, sodium or potassium, but is preferably sodium or potassium, more preferably potassium.

[0031] According to the production method of the present invention, the mixture obtained in step 1 is contacted with the amine as a raw material for step 2 without separation and reacted therewith, eliminating the need to separate the mixture obtained in step 1. Separation not only complicates the operation and increases the operation cost, but also adversely affects the yield of the target product due to loss of material during separation. According to the production method of the present invention, the mixture obtained in step 1 is used in step 2 without separation, thus simplifying the operation, reducing costs, and not adversely affecting the yield of the target product.

[0032] According to the production method of the present invention, in Formula 2-2-1 and Formula 2-2-2, R 201 , R 202 , R 203 , R204 , and R 205 are R1, R2, R3, R4, R5, R6, R7, R8, R9, and R of the compound of formula I. 10 and specific examples thereof give compounds of formula I, which will not be described in detail here.

[0033] According to the production method of the present invention, in Formula 2-3, R 206 , R 207 , R 208 , R 209 , R 210 , and R 211 is the R of the compound of formula I 11 , R 12 , R 13 , R 14 , R 15 , and R 16 and specific examples thereof give compounds of formula I, which will not be described in detail here.

[0034] According to the production method of the present invention, in step 1, a precursor compound is contacted with the heterocyclic compound in the presence of an organolithium compound, preferably an organomonolithium compound, more preferably a compound represented by formula VIII. R 26 Li (Formula VIII) In Formula VIII, R 26 is C1~C 10 alkyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl (including the various isomers of hexyl), heptyl (including the various isomers of heptyl), octyl (including the various isomers of octyl), nonyl (including the various isomers of nonyl), or decyl (including the various isomers of decyl).

[0035] Specific examples of the organolithium may include, but are not limited to, one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and isobutyllithium.

[0036] Preferably, the organolithium is one or more selected from the group consisting of n-butyllithium, sec-butyllithium, isobutyllithium, and tert-butyllithium, and more preferably, n-butyllithium.

[0037] In step 1, the contact temperature between the precursor compound and the heterocyclic compound may be 0 to 65°C, and the duration of the contact may be 1 to 120 hours, preferably 1.2 to 80 hours, more preferably 1.5 to 40 hours, and even more preferably 2 to 10 hours. In step 1, the precursor compound and the lithium salt of the heterocyclic compound are contacted in a first solvent, and the first solvent is preferably one or more of tetrahydrofuran, ethyl ether, dioxane, and hexane. The precursor compound and the heterocyclic compound are each mixed with a portion of the first solvent to form a solution, and the solution containing the precursor compound is mixed with a solution containing the heterocyclic compound, thereby contacting and reacting the precursor compound with the lithium salt of the heterocyclic compound.

[0038] In step 1, preferably, an organolithium is first contacted with the heterocyclic compound to form a lithium salt, which is then contacted with the precursor compound, the structure of which is shown in Formula 2-4. [ka]

[0039] The heterocyclic compound may be dissolved in a first solvent, placed in an environment of −78° C. to 0° C., and then an alkyllithium may be added to cause a reaction. The temperature for the reaction between the heterocyclic compound and the alkyllithium is preferably −78° C. to 60° C., more preferably −50° C. to 50° C., and even more preferably −10° C. to 30° C., and the reaction time is preferably 0.8 to 10 hours, more preferably 0.8 to 8 hours, and even more preferably 1 to 5 hours.

[0040] According to the production method of the present invention, in step 1, the mixture formed by contacting the precursor compound with the heterocyclic compound is contacted with the amine in step 2 without separation, thereby obtaining the metallocene complex of the present invention. According to the production method of the present invention, in step 2, the mixture obtained in step 1 and the amine are contacted preferably in a second solvent, and the second solvent is preferably one or more of toluene, xylene, and chlorobenzene. Preferably, at least a portion of the first solvent in the mixture obtained by contacting in step 1 is removed to obtain a mixture from which at least a portion of the first solvent has been removed, and the mixture from which at least a portion of the first solvent has been removed is mixed with a second solvent, thereby performing the contacting in step 2 in the second solvent.

[0041] According to the production method of the present invention, in step 2, the mixture obtained in step 1 and the amine may be contacted at a temperature of 0 to 30°C, and the duration of the contact may be 1 to 48 hours.

[0042] According to the production method of the present invention, the metallocene complex of the present invention may be separated from the mixture obtained in step 2 by a conventional method. In a preferred embodiment, at least a portion of the second solvent in the reaction mixture obtained in step 2 is removed, a third solvent is added to the reaction mixture from which at least a portion of the second solvent has been removed, followed by solid-liquid separation, collecting the liquid phase material, and removing the solvent from the liquid phase material. The remaining solid phase material is the metallocene complex of the present invention. The third solvent may be one or more of hexane, heptane, and toluene.

[0043] According to a third aspect of the present invention, there is provided a catalyst composition comprising a metallocene complex and a co-catalyst, wherein the metallocene complex is the metallocene complex according to the first aspect of the present invention.

[0044] According to the catalyst composition of the present invention, the cocatalyst may be a cocatalyst commonly used in the field of olefin polymerization. In a preferred embodiment, the cocatalyst is an organoaluminum compound and / or an organoboron compound.

[0045] The organoaluminum compound is preferably an aluminoxane and / or a compound of formula V: [ka] (In Formula V, R 17 , R 18 , and R 19 are the same or different and each independently represent hydrogen, C1 to C 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C7-C 15 Alkaryl, C7~C 15 and a hydrogen atom, and R 17 , R 18 , and R 19 is not a hydrogen atom at the same time.)

[0046] Above C1~C 10 The alkyl is C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl and C3-C 10and specific examples may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, decyl and its various isomers, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0047] Above C1~C 10 Illustrative examples of alkoxy may include, but are not limited to, methoxy, ethoxy, propoxy, and butoxy.

[0048] Said C6~C 20 Specific examples of aryl may include, but are not limited to, phenyl, tolyl, ethylphenyl, propylphenyl (wherein propyl may be n-propyl or isopropyl), butylphenyl (wherein butyl may be n-butyl, sec-butyl, isobutyl, or tert-butyl), naphthyl, anthracenyl, or phenanthrenyl.

[0049] The alkaryl is an aryl having an alkyl substituent, and specific examples of the alkaryl may include, but are not limited to, tolyl, ethylphenyl, dimethylphenyl, and diethylphenyl.

[0050] The aralkyl is an alkyl having an aryl substituent, and specific examples of the aralkyl may include, but are not limited to, benzyl, phenethyl, 1-phenylpropyl, 2-phenylpropyl, and 3-phenylpropyl.

[0051] Specific examples of the organoaluminum compound include diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, di(p-tolyl)aluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, ethylaluminum dihydride, butylaluminum dihydride, and isobutylaluminum dihydride. Aluminum hydride may include, but is not limited to, aluminum hydride, octylaluminum dihydride, pentylaluminum dihydride, diethylaluminum ethoxide, dipropylaluminum ethoxide, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri(p-tolyl)aluminum, tribenzylaluminum, ethyldiphenylaluminum, ethyldi(p-tolyl)aluminum, ethyldi(benzyl)aluminum, diethylphenylaluminum, diethyl-p-(tolyl)aluminum, and diethylbenzylaluminum.

[0052] In one preferred example, in formula V, R 17 , R 18 , and R 19 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl, and R 17 , R 18 , and R 19 More preferably, in formula V, at most one of R 17 , R18 , and R 19 is hydrogen or butyl, and R 17 , R 18 , and R 19 At most one of the atoms is hydrogen.

[0053] According to the catalyst composition of the present invention, the organoaluminum compound is preferably triisobutylaluminum and / or diisobutylaluminum hydride.

[0054] The organic boron compound is preferably an organic borate, which is an ionic compound consisting of a borate anion and a cation.

[0055] Specific examples of the borate anion may include, but are not limited to, tetraphenylborate, tetra(monofluorophenyl)borate, tetra(difluorophenyl)borate, tetra(trifluorophenyl)borate, tetra(tetrafluorophenyl)borate, tetra(pentafluorophenyl)borate, tetra(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, tetra(nitrilyl)borate, (triphenyl-pentafluorophenyl)borate, [tri(pentafluorophenyl)phenyl]borate, and undecahydro-7,8-dicarbonundecaborate.

[0056] Specific examples of the cations include, but are not limited to, carbonium cations, oxonium cations, ammonium cations, phosphine cations, cycloheptatrienyl cations, and ferrocenium cations containing transition metals. Among these, carbonium cations include trisubstituted carbonium cations, such as triphenylcarbonium cation and tri(substituted phenyl)carbonium cation. A more specific example of the tri(substituted phenyl)carbonium cation is tri(tolyl)carbonium cation. Specific examples of ammonium cations include trialkylammonium cations, such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N,N-dialkylanilinium cations, such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations, such as diisopropylammonium cation and dicyclohexylammonium cation. Specific examples of phosphine cations may include, but are not limited to, triaryl cations, such as triphenylphosphine cation, tri(tolyl)phosphine cation, and tri(nitrile)phosphine cation.

[0057] According to the catalyst composition of the present invention, the organoboron compound is preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethylium tetrakis(pentafluorophenyl)borate.

[0058] According to the catalyst composition of the present invention, the organoaluminum compound and the organoboron compound, which are co-catalysts, may be used individually or in combination.

[0059] In a preferred embodiment, the co-catalyst is an organoaluminum compound and an organoboron compound. In this preferred embodiment, the co-catalyst is more preferably triisobutylaluminum and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. In this preferred embodiment, the molar ratio of the organoaluminum compound to the organoboron compound in the co-catalyst may be 1:0.01-100, preferably 1:0.1-90, more preferably 1:0.5-60, where the organoaluminum compound is calculated in terms of elemental aluminum, and the organoboron compound is calculated in terms of elemental boron. In this preferred embodiment, the amount of the co-catalyst used may be a commonly used amount. When the co-catalyst contains an organoboron compound, the molar ratio of the metallocene complex to the organoboron compound is preferably 1:0.1-10, more preferably 1:0.5-5.

[0060] According to a fourth aspect of the present invention, there is provided a process for polymerising olefins, comprising the step of contacting at least one olefin with components in a catalyst composition under olefin polymerisation reaction conditions, said catalyst composition being the catalyst composition according to the third aspect of the present invention.

[0061] The olefin polymerization method according to the present invention is particularly suitable for copolymerization of ethylene and a conjugated diolefin. In a preferred embodiment of the olefin polymerization method according to the present invention, the olefin is a conjugated diolefin. In another preferred embodiment, the olefin is ethylene and a conjugated diolefin.

[0062] The conjugated diolefin is a compound containing a conjugated double bond in its molecular structure, and may be one or more compounds selected from the compounds represented by formula VI: [ka] (In Formula VI, R 20 , R 21 , and R 22are the same or different and are each selected from hydrogen and C1 to C5 linear or branched alkyl.

[0063] In the olefin polymerization method according to the present invention, specific examples of the conjugated diolefin may include, but are not limited to, butadiene and / or isoprene, and preferably, the conjugated diolefin is butadiene.

[0064] In the olefin polymerization method according to the present invention, the amount of the metallocene complex used in the catalyst composition is preferably 0.1 to 1000 μmol per 1 mol of the conjugated diolefin.

[0065] In the olefin polymerization method according to the present invention, the contacting may be carried out at a temperature of from -100°C to 150°C, but is preferably carried out at a temperature of from 10 to 50°C.

[0066] According to a fifth aspect of the present invention, there is provided an olefin polymer produced by the method according to the third aspect of the present invention.

[0067] In a preferred embodiment, the olefin polymer contains ethylene structural units derived from ethylene and conjugated diolefin structural units derived from a conjugated diolefin. In this preferred embodiment, the content of the ethylene structural units may be 80 mol% or less, preferably 5 to 70 mol%, and more preferably 10 to 60 mol%, based on the total amount of the olefin polymer. In this preferred embodiment, the content of cis 1,4-structural units in the structural units derived from the conjugated diolefin is preferably 85 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 98 mol% or more. In this preferred embodiment, the conjugated diolefin is preferably butadiene. In the present invention, a cis structural unit is a structural unit in a cis configuration in a conjugated diolefin structural unit, and a cis 1,4-structural unit is a structural unit in a cis configuration formed in a 1,4-polymerization form of a conjugated diolefin.

[0068] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0069] In the following examples and comparative examples, the molecular weight and molecular weight distribution index (Mw / Mn) of the polymer were measured using an Agilent 1260 Infinity II high-temperature gel permeation chromatograph. The chromatography columns used were two MIXD-B columns (300 x 7.5 mm) and one Guard column (50 x 7.5 mm). The mobile phase was trichlorobenzene, the flow rate was 1 mL / min, the sample solution concentration was 1 mg / mL, the injection volume was 200 μL, and the test temperature was 150°C. Monodisperse polystyrene was used as a standard sample.

[0070] In the following examples and comparative examples, nuclear magnetic resonance spectroscopy tests were carried out using a 400 MHz nuclear magnetic resonance apparatus purchased from Bruker. In the case of polybutadiene, tests were carried out at room temperature using deuterated chloroform as a solvent and tetramethylsilane (TMS) as an internal standard, and in the case of ethylene-butadiene copolymers, tests were carried out at a temperature of 100°C using deuterated tetrachloroethane as a solvent. The content of cis-1,4 structural units in butadiene structural units was determined by the content of the cis-1,4 structural unit in the polymer. 13 Calculated based on the C NMR spectrum, the peak at 26.5 to 27.5 ppm corresponds to the carbon atoms in the cis-1,4 structural unit, and the peaks at 26.5 to 27.5 ppm and 31.5 to 32.5 ppm correspond to the carbon atoms in the butadiene structural unit. The content of the ethylene structural unit in the copolymer is 13 Calculations were made based on the C NMR spectrum, with the peak at 28.5 to 30.0 ppm corresponding to the carbon atoms in the ethylene structural unit, and the peaks at 26.5 to 27.5 ppm and 31.5 to 32.5 ppm corresponding to the carbon atoms in the butadiene structural unit. The cis structural unit refers to a structural unit with a cis configuration, and the cis 1,4-structural unit refers to a structural unit with a cis configuration formed by 1,4-polymerization of butadiene.

[0071] In the following examples and comparative examples, the monomer conversion rate is calculated by the following formula: Monomer conversion rate (%)=mass of obtained polymer / mass of added monomer×100%.

[0072] Preparation Examples 1 to 4 are used to prepare metallocene complexes according to the present invention. Manufacturing Example 1

[0073] Synthesis of bis(2-methyl-3,5-diphenyl-6-hydro-cyclopentadienothiophene)gadolinium bis(trimethylsilylamide) (complex represented by formula II) [ka] Under a nitrogen atmosphere, 20 mL of a THF solution containing 2-methyl-3,5-diphenyl-6-hydrocyclopentadienothiophene and n-butyllithium (1.819 g, 6.2 mmol) was slowly added dropwise to 40 mL of a THF solution of GdCl3 (0.791 g, 3 mmol). The mixture was then stirred at 65 °C for 6 hours. The THF was then evaporated under reduced pressure, and 50 mL of toluene was added. 20 mL of a toluene solution of KN(SiMe3)2 (0.519 g, 2.6 mmol) was then slowly added dropwise to the mixture, followed by stirring at room temperature (25 °C) for 12 hours. The toluene was then evaporated under reduced pressure, 100 mL of hexane was added, and the precipitate was removed by filtration. The hexane was then evaporated under reduced pressure to obtain the desired product (1.336 g, 50% yield) as a pale yellow solid. The product was analyzed by elemental analysis, and the results are as follows: C 61.91;H 5.42. Manufacturing Example 2

[0074] Synthesis of bis(2,5-dimethyl-3-phenyl-6-hydro-cyclopentadienothiophene)scandium bis(dimethylsilylamide) (complex represented by formula III) [ka] GdCl3 of Preparation Example 1 was replaced with ScCl 3、The metallocene complex was prepared in the same manner as in Preparation Example 1, except that 2-methyl-3,5-diphenyl-6-hydrocyclopentadienothiophene was replaced with 2,5-dimethyl-3-phenyl-6-hydrocyclopentadienothiophene and KN(SiMe3)2 was replaced with KN(SiMe2H)2, and the target product was obtained as a pale yellow solid (1.183 g, yield: 63%). Elemental analysis of the product gave the following results: C 65.91; H 6.76. Manufacturing Example 3

[0075] Synthesis of bis(2-methyl-3-phenyl-5-isopropyl-6-hydro-cyclopentadienothiophene)gadolinium bis(trimethylsilylamide) (complex represented by formula IV) [ka] A metallocene complex was prepared in the same manner as in Preparation Example 1, except that 2-methyl-3,5-diphenyl-6-hydrocyclopentadienothiophene was replaced with 2-methyl-3-phenyl-5-isopropyl-6-hydrocyclopentadienothiophene, and the target product was obtained as a white solid (1.357 g, yield: 55%). The product was analyzed by elemental analysis, and the obtained elemental analysis results were as follows: C 58.28; H 6.36. Production Example 4

[0076] Synthesis of bis(2,5-dimethyl-3-phenyl-4-trimethylsilyl-6-hydro-cyclopentadienothiophene)gadolinium bis(trimethylsilylamide) (complex represented by formula V) [ka] A metallocene complex was prepared in the same manner as in Preparation Example 1, except that 2,5-dimethyl-3-phenyl-4-trimethylsilyl-6-hydrocyclopentadienothiophene was used instead of 2-methyl-3,5-diphenyl-6-hydrocyclopentadienothiophene, and the target product was obtained as a white solid (1.232 g, yield: 45%). The product was analyzed by elemental analysis, and the obtained elemental analysis results were as follows: C 55.27; H 6.63. Comparative Manufacturing Example 1

[0077] Complex VI was synthesized by the method described in Dalton Trans., 2008, 2531-2533. [ka] Comparative Manufacturing Example 2

[0078] Complex VII was synthesized by the method described in Angew. Chem. Int. Ed., 2017(56), 6975-6979. [ka] Examples 1 to 10 illustrate the olefin polymerization process using the catalyst composition of the present invention, as well as the olefin polymers. Example 1

[0079] In a glove box protected by an argon atmosphere, 4.46 mg of the complex represented by Formula II and 4.00 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of a 1 M triisobutylaluminum hexane solution was added. After complete dissolution, 3.5 mL of a toluene solution of butadiene (containing 0.54 g of butadiene) was added. Polymerization was carried out at room temperature (25°C) for 1 hour. After polymerization was completed, the reaction was stopped by adding a small amount of methanol containing hydrochloric acid. The product was poured into a large amount of ethanol, and the polymer was isolated and washed with ethanol. The product was dried in a vacuum oven until no weight loss was observed, thereby obtaining polybutadiene. The monomer conversion was calculated to be 100%, and GPC analysis showed that this polymer had a number average molecular weight (M n ) is 112,000, and the molecular weight distribution index (M w / M n ) is 1.2. Analysis by nuclear magnetic resonance spectroscopy shows that the molar content of cis 1,4-structural units in the resulting polybutadiene is greater than 99%. Example 2

[0080] In a glove box protected by an argon atmosphere, 30.34 mg of the complex represented by Formula II and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added sequentially to a 500 mL autoclave. Ethylene was then introduced at 0.8 MPa, and once saturated, the catalyst solution was added. Polymerization was carried out at 40°C for 60 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt %, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 14.6 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n) is 105,000, and the molecular weight distribution index (M w / M n ) is 1.6. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 86.2%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 95.2%. Example 3

[0081] In a glove box protected by an argon atmosphere, 28.03 mg of the complex represented by Formula III and 31.36 mg of triphenylmethylium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added sequentially to a 500 mL autoclave. Ethylene was then introduced at 0.8 MPa, and once saturated, the catalyst solution was added. Polymerization was carried out at room temperature (25°C) for 180 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 13.2 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n ) is 131,000, and the molecular weight distribution index (M w / M n ) is 3.7. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 65.2%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 90.5%. Example 4

[0082] In a glove box protected by an argon atmosphere, 4.12 mg of the complex represented by Formula IV and 4.00 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of a 1 M triisobutylaluminum hexane solution was added. After complete dissolution, 3.5 mL of a toluene solution of butadiene (containing 0.54 g of butadiene) was added. Polymerization was carried out at room temperature (25°C) for 2 hours. After polymerization was completed, the reaction was stopped by adding a small amount of methanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was isolated and washed with ethanol. The product was dried in a vacuum oven until no weight loss was observed, thereby obtaining polybutadiene. The monomer conversion was calculated to be 100%, and GPC analysis showed that this polymer had a number average molecular weight (M n ) is 101000, and the molecular weight distribution index (M w / M n ) is 1.4. Analysis by nuclear magnetic resonance spectroscopy shows that the molar content of cis 1,4-structural units in the resulting polybutadiene is greater than 99%. Example 5

[0083] In a glove box protected by an argon atmosphere, 31.03 mg of the complex represented by formula V and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M diisobutylaluminum hydride hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a diisobutylaluminum hydride solution. 120 g of toluene, the diisobutylaluminum hydride solution, and 14 g of butadiene were added sequentially to a 500 mL autoclave. Ethylene was then introduced at 0.8 MPa, and once saturated, the catalyst solution was added. Polymerization was carried out at room temperature (25°C) for 180 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 12.1 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n ) is 288,000, and the molecular weight distribution index (M w / M n ) is 2.4. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 78.3%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was greater than 99%. Example 6

[0084] In a glove box protected by an argon atmosphere, 28.03 mg of the complex represented by Formula III and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added, in that order, to a 500 mL autoclave. Then, 1.2 MPa of ethylene was introduced, and once saturated, the catalyst solution was added. Polymerization was carried out at 40°C for 60 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt %, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 6.5 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n ) is 123,000, and the molecular weight distribution index (M w / M n ) is 3.1. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 48.4%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 90.2%. Example 7

[0085] In a glove box protected by an argon atmosphere, 30.34 mg of the complex represented by Formula II and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added sequentially to a 500 mL autoclave. Ethylene was then introduced at 0.8 MPa, and once saturated, the catalyst solution was added. Polymerization was carried out at room temperature (25°C) for 180 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 5.14 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n ) is 83,000, and the molecular weight distribution index (M w / M n ) is 2.7. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 85.6%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 98.5%. Comparative Example 1

[0086] A copolymer (13.8 g) was obtained in the same manner as in Example 2, except that the complex represented by formula II was replaced with the metallocene complex VI prepared in Comparative Preparation Example 1. The copolymer had a number average molecular weight (M n ) is 96,000, and the molecular weight distribution index (M w / M n ) is 1.7. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 82%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 91.3%. Example 8

[0087] In a glove box protected by an argon atmosphere, 22.24 mg of the complex represented by Formula III and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added sequentially to a 500 mL autoclave. Ethylene was then introduced at 0.8 MPa, and once saturated, the catalyst solution was added. Polymerization was carried out at 40°C for 60 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt %, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 8.70 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n ) is 112,000, and the molecular weight distribution index (M w / M n ) is 2.5. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 65.3%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 88.4%. Comparative Example 2

[0088] In a glove box protected by an argon atmosphere, 17.50 mg of the complex represented by Formula VII and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. 2 mL of a 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to a separate glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added sequentially to a 500 mL autoclave. Ethylene was then introduced at 0.8 MPa, and once saturated, the catalyst solution was added. Polymerization was carried out at 40°C for 60 minutes. After polymerization was complete, the product was precipitated by pouring it into a large amount of ethanol containing hydrochloric acid (2 wt %, hydrochloric acid is calculated as HCl). The copolymer was separated by filtration and washed with ethanol. The copolymer was dried in a vacuum oven until no weight loss was observed, thereby obtaining 4.81 g of copolymer. GPC analysis showed that this copolymer had a number average molecular weight (M n ) is 105,000, and the molecular weight distribution index (M w / M n ) is 2.3. Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in this copolymer was 71.5%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, was 86.3%. Example 9

[0089] In a glove box protected by an argon atmosphere, 4.12 mg of the complex represented by formula III and 4.61 mg of triphenylmethylium tetrakis(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of a 1 M triisobutylaluminum hexane solution was added. After complete dissolution, 3.5 mL of a toluene solution of butadiene (containing 0.54 g of butadiene) was added. Polymerization was carried out at room temperature (25°C) for 2 hours. After polymerization was completed, the reaction was stopped by adding a small amount of methanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was isolated and washed with ethanol. The product was dried in a vacuum oven until no weight loss was observed, thereby obtaining polybutadiene. The monomer conversion was calculated to be 100%, and GPC analysis showed that this polymer had a number average molecular weight (M n ) is 145,000, and the molecular weight distribution index (M w / M n ) is 1.4. Analysis by nuclear magnetic resonance spectroscopy reveals that the molar content of cis 1,4-structural units in the resulting polybutadiene is 91.5%. Example 10

[0090] In a glove box protected by an argon atmosphere, 4.56 mg of the complex represented by formula V and 4.00 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of a 1 M triisobutylaluminum hexane solution was added. After complete dissolution, 3.5 mL of a toluene solution of butadiene (containing 0.54 g of butadiene) was added. Polymerization was carried out at room temperature (25°C) for 2 hours. After polymerization was completed, the reaction was stopped by adding a small amount of methanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was isolated and washed with ethanol. The product was dried in a vacuum oven until no weight loss was observed, thereby obtaining polybutadiene. The monomer conversion was calculated to be 100%, and GPC analysis showed that this polymer had a number average molecular weight (M n ) is 125,000, and the molecular weight distribution index (M w / M n) is 1.3. Analysis by nuclear magnetic resonance spectroscopy shows that the molar content of cis 1,4-structural units in the resulting polybutadiene is greater than 99%. Comparative Example 3

[0091] In a glove box protected by an argon atmosphere, 3.50 mg of the complex represented by formula VI and 4.00 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of a 1 M triisobutylaluminum hexane solution was added. After complete dissolution, 3.5 mL of a toluene solution of butadiene (containing 0.54 g of butadiene) was added. Polymerization was carried out at room temperature (25°C) for 2 hours. After polymerization was completed, the reaction was stopped by adding a small amount of hydrochloric acid-containing methanol (2 wt%, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was isolated and washed with ethanol. The product was dried in a vacuum oven until no weight loss was observed, thereby obtaining polybutadiene. The monomer conversion rate was 96.3%, and as measured by GPC analysis, this polymer had a number average molecular weight (M n ) is 125,000, and the molecular weight distribution index (M w / M n ) is 1.2. Analysis by nuclear magnetic resonance spectroscopy shows that the molar content of cis 1,4-structural units in the resulting polybutadiene is greater than 99%. Comparative Example 4

[0092] In a glove box protected by an argon atmosphere, 2.93 mg of the complex represented by Formula VII and 4.61 mg of triphenylmethylium tetrakis(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of a 1 M triisobutylaluminum hexane solution was added. After complete dissolution, 3.5 mL of a toluene solution of butadiene (containing 0.54 g of butadiene) was added. Polymerization was carried out at room temperature (25°C) for 2 hours. After polymerization was completed, the reaction was stopped by adding a small amount of methanol containing hydrochloric acid (2 wt%, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was isolated and washed with ethanol. The product was dried in a vacuum oven until no weight loss was observed, thereby obtaining polybutadiene. The monomer conversion was calculated to be 100%, and GPC analysis showed that this polymer had a number average molecular weight (M n ) is 123,000, and the molecular weight distribution index (M w / M n ) is 1.4. Analysis by nuclear magnetic resonance spectroscopy reveals that the molar content of cis 1,4-structural units in the resulting polybutadiene is 85.3%.

[0093] The experimental results of Examples 1 to 10 demonstrate that the metallocene complex of the present invention exhibits improved catalytic activity and results in higher polymer yields. The metallocene complex of the present invention can polymerize conjugated diolefins efficiently and regioselectively. When used in the copolymerization reaction of ethylene and conjugated diolefin, the metallocene complex of the present invention can effectively copolymerize ethylene-conjugated diolefin and efficiently control the copolymer composition of the copolymer.

[0094] Comparisons between Example 2 and Comparative Example 1, Example 8 and Comparative Example 2, and Example 1 and Comparative Examples 3 and 4 reveal that under the same conditions, the polymerization method of the present invention produces a larger amount of copolymer. This demonstrates that the transition metal complex used in the polymerization method of the present invention has higher catalytic activity and can therefore achieve high polymerization reaction efficiency.

[0095] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the technical spirit of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining various technical features in other appropriate ways. These simple modifications and combinations are also considered to be the disclosure content of the present disclosure and fall within the protection scope of the present disclosure.

Claims

1. A metallocene complex having the structure shown in Formula I: 【Chemistry 1】 In Formula I, Ln is a lanthanide, scandium, or yttrium; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , and R １０ are the same or different and each independently represent hydrogen, C １ ~C ２０ Alkyl, C ６ ~C ３０ aryl of the formula -SiR ２３ R ２４ R ２５ and R ２３ , R ２４ , and R ２５ are the same or different and each independently represent hydrogen or C １ ~C ２０ is an alkyl of R １１ , R １２ , R １３ , R １４ , R １５ , and R １６ are the same or different and each independently represent hydrogen or C １ ~C ５ is an alkyl of E is O, S, or N-R １７ and R １７ is C １ ~C ５ alkyl or C ６ ~C １２ is an aryl of

2. In Formula I, R １ , and R ６ are each independently C １ ~C ５ and R ２ , R ４ , R ７ , and R ９ are each independently C ６ ~C １２ and R ３ , R ５ , R ８ , and R １０ 3. The metallocene complex of claim 1, wherein all of are hydrogen.

3. The metallocene complex of claim 2, wherein R 1 and R 6 are methyl, and R 2 , R 4 , R 7 and R 9 are phenyl.

4. In Formula I, R １ , R ４ , R ６ , and R ９ are each independently C １ ~C ２０ and R ２ , and R ７ are each independently C ６ ~C ３０ and R ３ , R ５ , R ８ , and R １０ 3. The metallocene complex of claim 1, wherein all of are hydrogen.

5. The metallocene complex according to claim 4, wherein R 1 , R 4 , R 6 , and R 9 are each independently a C 1 to C 5 alkyl, and R 2 and R 7 are each independently a C 6 to C 12 aryl.

6. The metallocene complex of claim 5, wherein R 1 , R 4 , R 6 , and R 9 are each independently methyl or isopropyl, and R 2 and R 7 are phenyl.

7. The metallocene complex according to claim 6, wherein R 1 and R 6 are methyl, R 4 and R 9 are methyl or isopropyl, and R 2 and R 7 are phenyl.

8. In Formula I, R １ , R ４ , R ６ , and R ９ are each independently C １ ~C ２０ and R ２ , and R ７ are each independently C ６ ~C ３０ and R ５ , and R １０ are all hydrogen, and R ３ , and R ８ are each independently —SiR ２３ R ２４ R ２５ and R ２３ , R ２４ , and R ２５ are the same or different, and each independently represents C １ ~C ２０ 2. The metallocene complex of claim 1, wherein the alkyl is:

9. The metallocene complex described in claim 8, wherein R 1, R 4, R 6, and R 9 are each independently C 1 to C 5 alkyl, R 2 and R 7 are each independently C 6 to C 12 aryl, R 3 and R 8 are each independently -SiR 23 R 24 R 25, R 23, R 24, and R 25 are the same or different and each independently hydrogen or C 1 to C 5 alkyl, and at least one of R 23, R 24, and R 25 is C 1 to C 5 alkyl.

10. The metallocene complex according to claim 9, wherein R 1 , R 4 , R 6 , and R 9 are methyl, R 2 and R 7 are phenyl, R 3 and R 8 are each independently -SiR 23 R 24 R 25 , and R 23 , R 24 , and R 25 are all methyl.

11. 2. The metallocene complex of claim 1, wherein in formula I, Ln is scandium or gadolinium.

12. 2. The metallocene complex of claim 1, which is a complex of Formula II, Formula III, Formula IV, or Formula V. 【Chemistry 2】

13. Step 1: contacting a precursor compound with a heterocyclic compound selected from the compounds of formula 2-2-1 and formula 2-2-2 in the presence of an organolithium; Step 2, contacting the mixture obtained in Step 1 with an amine represented by formula 2-3; The precursor compound is selected from compounds represented by formula 2-1: LnX (Formula 2-1) In Formula 2-1, Ln is a lanthanide, scandium, or yttrium; X is a halogen atom; 【Transformation 3】 In Formula 2-2-1 and Formula 2-2-2, R ２０１ , R ２０２ , R ２０３ , R ２０４ , and R ２０５ are the same or different and each independently represent hydrogen, C １ ~C ２０ Alkyl, C ６ ~C ３０ aryl of the formula -SiR ２３ R ２４ R ２５ and R ２３ , R ２４ , and R ２５ are the same or different and each independently represent hydrogen or C １ ~C ２０ is an alkyl of In Formula 2-2-1 and Formula 2-2-2, E is O, S, or N—R １７ and R １７ is C １ ~C ５ Alkyl, C ６ ~C １２ is an aryl of 【Chemistry 4】 In Formula 2-3, R ２０６ , R ２０７ , R ２０８ , R ２０９ , R ２１０ , and R ２１１ are the same or different and each independently represent hydrogen or C １ ~C ５ is an alkyl of 2. The method for producing a metallocene complex according to claim 1, wherein M is an alkali metal atom.

14. The mixture contacted in step 1 is used in step 2 without separation; and / or the contacting in step 1 is carried out in a first solvent and the contacting in step 2 is carried out in a second solvent, the first solvent and the second solvent being different; 14. The method of claim 13, further comprising the steps of removing at least a portion of the first solvent from the mixture contacted in step 1 to obtain a mixture from which at least a portion of the first solvent has been removed, and mixing the mixture from which at least a portion of the first solvent has been removed with the second solvent.

15. The method described in claim 14, wherein the first solvent is one or more selected from the group consisting of tetrahydrofuran, ethyl ether, dioxane, and hexane, and the second solvent is one or more selected from the group consisting of toluene, xylene, and chlorobenzene.

16. 14. The method of claim 13, wherein step 1 comprises contacting an organolithium with a heterocyclic compound of formula 2-2 to form a lithium salt, and contacting the lithium salt with the precursor compound.

17. In step 1, the contacting is carried out at a temperature of 0 to 65° C., and in step 1, the duration of the contacting is 1 to 120 hours; 14. The method of claim 13, wherein in step 2, the contacting is carried out at a temperature of 0 to 30°C, and in step 2, the duration of the contacting is 1 to 48 hours.

18. A catalyst composition comprising a metallocene complex and a cocatalyst, wherein the metallocene complex is the metallocene complex according to any one of claims 1 to 12.

19. the co-catalyst is an organoaluminum compound and / or an organoboron compound; The organoaluminum compound is an aluminoxane and / or a compound represented by formula V:

20. The catalyst composition of claim 18, wherein the organoboron compound is an organoborate. 【Transformation 5】 (In Formula V, R １７ , R １８ , and R １９ are the same or different and each independently represent hydrogen, C １ ~C １０ Alkyl, C １ ~C １０ Alkoxy, C ６ ~C ２０ Aryl of C ７ ~C １５ Alkhalil, C ７ ~C １５ and a hydrogen atom, and R １７ , R １８ , and R １９ cannot be a hydrogen atom at the same time.)

20. The organoaluminum compound is triisobutylaluminum and / or diisobutylaluminum hydride, and / or the organoboron compound is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethylium tetrakis(pentafluorophenyl)borate. Catalyst composition according to claim 19,

21. the co-catalyst is an organoaluminum compound and an organoboron compound, the organoaluminum compound is triisobutylaluminum and / or diisobutylaluminum hydride, and the organoboron compound is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethylium tetrakis(pentafluorophenyl)borate; and / or, in the co-catalyst, the molar ratio of the organoaluminum compound to the organoboron compound is 1:0.01 to 100, the organoaluminum compound is calculated in terms of elemental aluminum, and the organoboron compound is calculated in terms of elemental boron; and / or the molar ratio of said metallocene complex to said organoboron cocatalyst is 1:0.1-10.

22. 20. A process for polymerizing olefins, comprising the step of contacting at least one olefin with each of the components in a catalyst composition under olefin polymerization reaction conditions, wherein the catalyst composition is the catalyst composition of claim 18.

23. 23. The method of claim 22, wherein the olefin is a conjugated diolefin or ethylene and a conjugated diolefin.

24. The method of claim 23, wherein the conjugated diolefin is butadiene and / or isoprene.

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