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 play a very important role as catalysts in various polymerization reactions. Due to different types of ligands and central metals, metallocene complexes show different catalytic properties in polymerization reactions.

[0004] Many proposals have been made regarding polymerization catalysts 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 mainly composed of a neodymium compound and an organoaluminum compound. Some of these polymers are industrially used as polymer catalyst systems for butadiene. However, there has been a demand for a method for efficiently producing conjugated diene polymers with a high content of cis 1,4 structures in the microstructure, a high molecular weight, and a narrow molecular weight distribution. Therefore, it is necessary to develop a polymerization catalyst.

[0005] Ethylene, a widely used and easily 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 for producing ethylene, was once traded at a price close to that of ethylene. Due to changes in the production route of ethylene, the production volume of butadiene decreased and the price rose significantly. Meanwhile, the price of ethylene fell. Therefore, the use of ethylene as a raw material for producing rubber for tires is highly promising, and it can save a lot of raw material costs. However, conjugated dienes and α-olefins are difficult to copolymerize because of their different polymerization mechanisms. Therefore, it has been a challenge to catalyze the copolymerization of ethylene and conjugated dienes using the same catalyst system, and traditionally, academic and industrial efforts have been made to realize the copolymerization of the two. It is highly promising to develop metallocene complexes with higher catalytic activity, higher controllability of the structural regularity of the conjugated diolefin structural unit, and higher copolymerization ability of ethylene and conjugated diolefin.

[0006] In 2015, Michiue et al. reported the production of ethylene / propylene and butadiene copolymers using a series of silicon-bridged disubstituted indenyl zirconium in the presence of hydrogen (K. Michiue, M. Mitani, T. Fujita, Catalysts 2015, 5, 2001-2017). The catalyst activity is high, and polymers with higher molecular weights can be obtained. As the steric hindrance of the substituents on the indene increases, the vinyl content in the copolymer increases. However, the resulting copolymer has a low insertion rate of butadiene, and furthermore, the copolymer contains cyclopropyl and cyclopentyl structures. Rare earth catalysts have good affinity for conjugated diolefins, so attempts have also been made to copolymerize ethylene and 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 is relatively high and exists mainly in the trans 1,4-structure. The molecular weight of the polymer is not sufficient, and the polymer contains cyclohexyl structures.

[0007] Transition metal compounds with heterocyclic fused five-membered ring π-ligands and their use as monoolefin polymerization catalysts with the advantages of high activity and high molecular weight have been reported. However, there are few reports on ethylene-conjugated diolefin copolymerization catalysts. 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 the conjugated diolefin structural unit, thereby improving the structural regularity of the conjugated diolefin structural unit in the produced polymer, and when used in the copolymerization of ethylene and a conjugated diolefin, can effectively control the copolymerization composition of the copolymer.

[0009] [Means for solving the problem] According to a first aspect, the present invention provides 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 represents hydrogen, C1 to C 20 Alkyl, C6-C 30 or -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-C 20 is an alkyl group 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-C5 alkyl or C6-C 12 is an aryl of

[0010] According to a second aspect of the present invention, there is provided a method for producing ... composition comprising the steps of: 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 represents hydrogen, C1 to C 20 Alkyl, C6-C 30 or -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-C 20 is an alkyl group 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 formula 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 process for the preparation of 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, said metallocene complex being a metallocene complex as defined in the first aspect of the present invention.

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

[0013] According to a fifth aspect of the present invention, the present invention provides an olefin polymer produced by the process according to the fourth aspect of the present invention.

[0014] [Effects of the invention] The catalyst composition containing the metallocene complex according to 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 conjugated diolefin. The catalyst composition containing the metallocene complex according to the present invention can precisely control the structure of the conjugated diolefin structural unit, thereby improving the structural regularity of the conjugated diolefin structural unit in the produced polymer. The catalyst system containing the metallocene complex according to the present invention has excellent copolymerizability, can efficiently realize the copolymerization of ethylene with conjugated diolefin, and can efficiently control the copolymerization composition of the copolymer. The method for producing the metallocene complex according to the present invention is a "one-pot method" for producing the metallocene complex, which efficiently simplifies the synthesis route, reduces the complexity of the operation, and reduces the operation cost.

[0015] [Mode for carrying out the invention] The range endpoints and any values ​​disclosed herein are not limited to the exact 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 the individual dot values, and the individual dot values ​​can be combined to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] According to a first aspect, the present invention provides 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 (number 57) to lutetium (number 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 represents hydrogen, C1 to C 20Alkyl, C6-C 30 or -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-C 20 Preferably, R 23 , R 24 , and R 25 At least one of C1 to C 20 is an alkyl group.

[0021] In the present invention, C1 to C 20 The alkyl group 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 30Illustrative 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 group, and R2, R4, R7, and R9 are each independently a C6-C 12 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 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 C7 alkyl. 12 More preferably, R1, R4, R6, and R9 are methyl or isopropyl, and R2 and R7 are phenyl. Even more preferably, R1 and R6 are methyl, R4, and R9 are methyl or isopropyl, and R2 and R7 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 R5 and R 10 are all hydrogen, and R and R 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 R and R 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 represents hydrogen or 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 one of R is C1-C5 alkyl. 14 , R 15 , and R 16 At least one of R is C1 to C5 alkyl. More 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 two of R are C1-C5 alkyl. 14 , R 15 , and R 16 At least two of R are C1-C5 alkyl. More 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 is 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-C5 alkyl or C6-C 12 Preferably, in formula I, E is S.

[0028] According to the metallocene complex of the present invention, said 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 producing ... composition comprising the steps of: Step 1, contacting a precursor compound with a heterocyclic compound selected from the compound represented by formula 2-2-1 and the compound represented by 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 represents hydrogen, C1 to C 20 Alkyl, C6-C 30 or -SiR23 R 24 R 25 and R 23 , R 24 , and R 25 are the same or different, and each independently represents hydrogen or C1-C 20 is an alkyl group 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 formula 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, There is provided a process for the preparation of a metallocene complex according to the first aspect of the present invention, 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, and the operation of separating the mixture obtained in step 1 is omitted. The separation operation not only complicates the operation and increases the operation cost, but also adversely affects the yield of the target product due to the loss of materials during the separation. According to the production method of the present invention, the mixture obtained in step 1 is used in step 2 without separation, thus not only simplifying the operation and reducing the cost, but also 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 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 are not 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 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 are not described in detail here.

[0034] According to the process of the present invention, in step 1, a precursor compound is contacted with the heterocyclic compound in the presence of an organolithium. The organolithium is 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. More preferably, the organolithium is 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, but is 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 part of the first solvent to form a solution, and the solution containing the precursor compound is mixed with the 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 reacted with an alkyllithium. 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 according to 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 preferably contacted in a second solvent, and the second solvent is preferably one or more of toluene, xylene, and chlorobenzene. Preferably, when at least a part of the first solvent in the mixture obtained by contacting in step 1 is removed, a mixture from which at least a part of the first solvent has been removed is obtained, and the mixture from which at least a part of the first solvent has been removed is mixed with a second solvent, thereby the contact in step 2 is performed 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 preparation 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 part 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 part of the second solvent has been removed, and then solid-liquid separation is performed, the liquid phase material is collected, and the solvent of the liquid phase material is removed, and 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, said metallocene complex being a metallocene complex as defined in 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 represents 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 group is C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, and C3-C 10and cycloalkyl, specific examples of which 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 Illustrative 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, 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, diethylp-(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 At most one of R is hydrogen. More preferably, in formula V, 17 , R18 , and R 19 is hydrogen or butyl, and R 17 , R 18 , and R 19 At most one of them 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(nitrile)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 them, the carbonium cations include tri-substituted carbonium cations, such as triphenylcarbonium cations and tri(substituted phenyl)carbonium cations. More specific examples of the tri(substituted phenyl)carbonium cations include tri(tolyl)carbonium cations. Specific examples of the ammonium cations include, but are not limited to, trialkylammonium cations, such as trimethylammonium cations, triethylammonium cations, tripropylammonium cations, and tributylammonium cations; N,N-dialkylanilinium cations, such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, and N,N-2,4,6-pentamethylanilinium cations; and dialkylammonium cations, such as diisopropylammonium cations and dicyclohexylammonium cations. 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 catalytic 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 co-catalysts, organoaluminum compound and organoboron compound, may be used individually or in combination.

[0059] In a preferred embodiment, the cocatalyst is an organoaluminum compound and an organoboron compound. In this preferred embodiment, the cocatalyst 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 cocatalyst may be 1:0.01-100, but is preferably 1:0.1-90, more preferably 1:0.5-60, and the organoaluminum compound is calculated in terms of aluminum element, and the organoboron compound is calculated in terms of boron element. In this preferred embodiment, the amount of the cocatalyst used may be a general amount. When the cocatalyst contains an organoboron compound, the molar ratio of the metallocene complex to the organoboron compound is preferably 1:0.1-10, preferably 1:0.5-5.

[0060] According to a fourth aspect of the present invention, there is provided a process for the polymerization of olefins comprising the step of contacting at least one olefin with components in a catalyst composition under olefin polymerization 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 as a copolymerization reaction 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. The conjugated diolefin 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. Preferably, the conjugated diolefin is butadiene.

[0064] In the olefin polymerization process 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 process 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 process according to the third aspect of the present invention.

[0067] In a preferred embodiment, the olefin polymer contains an ethylene structural unit derived from ethylene and a conjugated diolefin structural unit derived from a conjugated diolefin. In this preferred embodiment, the content of the ethylene structural unit may be 80 mol% or less, preferably 5 to 70 mol%, more preferably 10 to 60 mol%, based on the total amount of the olefin polymer. In this preferred embodiment, the content of the cis 1,4-structural unit in the structural unit 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, the cis structural unit is a structural unit of cis configuration in the conjugated diolefin structural unit, and the cis 1,4-structural unit is a structural unit of cis configuration formed in the form of 1,4-polymerization of the 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 (300×7.5 mm) and one Guard column (50×7.5 mm). The mobile phase was trichlorobenzene, the flow rate was 1 mL / min, the concentration of the sample solution was 1 mg / mL, the injection amount 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, the nuclear magnetic resonance spectroscopy test was performed using a 400 MHz nuclear magnetic resonance apparatus purchased from Bruker. In the case of polybutadiene, the test was performed at room temperature using deuterated chloroform as a solvent and tetramethylsilane (TMS) as an internal standard, and in the case of ethylene-butadiene copolymer, the test was performed at a temperature of 100° C. using deuterated tetrachloroethane as a solvent. The content of cis-1,4 structural units in the butadiene structural units was determined by the following formula: 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 of the butadiene structural unit. The content of the ethylene structural unit in the copolymer is 13 Calculated based on the C NMR spectrum, the peak at 28.5 to 30.0 ppm corresponds to the carbon in the ethylene structural unit, and the peaks at 26.5 to 27.5 ppm and 31.5 to 32.5 ppm correspond to the carbon atoms of the butadiene structural unit. The cis structural unit refers to a structural unit in a cis configuration, and the cis 1,4-structural unit refers to a structural unit in a cis configuration formed by 1,4-polymerization of butadiene.

[0071] In the following Examples and Comparative Examples, the monomer conversion is calculated by the following formula: Monomer conversion (%)=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), a complex represented by formula II [ka] Under a nitrogen atmosphere, 20 mL of a THF solution containing 2-methyl-3,5-diphenyl-6-hydro-cyclopentadienothiophene and a lithium salt (1.819 g, 6.2 mmol) synthesized from n-butyl lithium was slowly added dropwise to 40 mL of a THF solution of GdCl3 (0.791 g, 3 mmol). The mixture was then stirred at a temperature of 65°C for 6 hours. Then, THF was evaporated under reduced pressure, and 50 mL of toluene was added. Then, 20 mL of a toluene solution of KN(SiMe3)2 (0.519 g, 2.6 mmol) was slowly added dropwise to the mixture, and the mixture was then stirred at room temperature (25°C) for 12 hours. Then, toluene was evaporated under reduced pressure, 100 mL of hexane was added, and the precipitate was removed by filtration. Then, hexane was evaporated under reduced pressure to obtain the target product (1.336 g, yield: 50%) as a light yellow solid. The product was analyzed through elemental analysis, and the results of the elemental analysis obtained were 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), a 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-hydro-cyclopentadienothiophene was replaced with 2,5-dimethyl-3-phenyl-6-hydro-cyclopentadienothiophene and KN(SiMe3)2 was replaced with KN(SiMe2H)2, and the target product was a light yellow solid (1.183 g, yield: 63%). The product was analyzed through elemental analysis, and the results of elemental analysis were as follows: C 65.91; H 6.76. Production Example 3

[0075] Synthesis of bis(2-methyl-3-phenyl-5-isopropyl-6-hydrocyclopentadienothiophene)gadolinium bis(trimethylsilylamide), a 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-hydro-cyclopentadienothiophene was used instead of 2-methyl-3-phenyl-5-isopropyl-6-hydro-cyclopentadienothiophene, and a white solid product (1.357 g, yield: 55%) was obtained. The product was analyzed through elemental analysis, and the results of elemental analysis 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-methyl-3,5-diphenyl-6-hydro-cyclopentadienothiophene was replaced with 2,5-dimethyl-3-phenyl-4-trimethylsilyl-6-hydro-cyclopentadienothiophene, and a white solid product (1.232 g, yield: 45%) was obtained. The product was analyzed through elemental analysis, and the results of the elemental analysis were as follows: C 55.27; H 6.63. Comparative Manufacturing Example 1

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

[0078] Complex VII was synthesized according to the method described in Angew. Chem. Int. Ed., 2017(56), 6975-6979. [ka] Examples 1 to 10 illustrate the olefin polymerization process and the olefin polymers produced using the catalyst composition of the present invention. 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 sufficient 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 the polymerization was completed, a small amount of methanol containing hydrochloric acid was added to stop the reaction. The product was poured into a large amount of ethanol, and the polymer was separated and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining polybutadiene. As a result of calculation, the conversion rate of the monomer was 100%, and as measured by GPC analysis, this polymer had a number average molecular weight (M n ) is 112000, and the molecular weight distribution index (M w / M n ) is 1.2. Nuclear magnetic resonance spectroscopy analysis 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 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to another glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 0.8 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 60 minutes at 40°C. After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 14.6 g of copolymer. When measured by GPC analysis, 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 shows that the molar content of butadiene structural units derived from butadiene in this copolymer is 86.2%, and the molar content of cis 1,4-structural units is 95.2%, based on the total amount of butadiene structural units. 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 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to another glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 0.8 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 180 minutes at room temperature (25 ° C.). After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 13.2 g of copolymer. When measured by GPC analysis, 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 shows that the molar content of butadiene structural units derived from butadiene in this copolymer is 65.2%, and the molar content of cis 1,4-structural units is 90.5%, based on the total amount of butadiene structural units. 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 sufficient 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 the polymerization was completed, a small amount of hydrochloric acid-containing methanol (2 wt %, hydrochloric acid is calculated as HCl) was added to stop the reaction. The product was poured into a large amount of ethanol, and the polymer was separated and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining polybutadiene. As a result of calculation, the conversion rate of the monomer was 100%, and as measured by GPC analysis, 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. Nuclear magnetic resonance spectroscopy analysis 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 1 M diisobutylaluminum hydride hexane solution and 7 mL of toluene were added to another glass bottle to obtain a diisobutylaluminum hydride solution. 120 g of toluene, the diisobutylaluminum hydride solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 0.8 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 180 minutes at room temperature (25 °C). After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 12.1 g of copolymer. When measured by GPC analysis, 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 reveals that the molar content of butadiene structural units derived from butadiene in this copolymer is 78.3%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, is 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 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to another glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 1.2 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 60 minutes at 40°C. After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 6.5 g of copolymer. When measured by GPC analysis, 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 reveals that the molar content of butadiene structural units derived from butadiene in this copolymer is 48.4%, and the molar content of cis 1,4-structural units, based on the total amount of butadiene structural units, is 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 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to another glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 0.8 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 180 minutes at room temperature (25 ° C.). After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 5.14 g of copolymer. When measured by GPC analysis, 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 shows that the molar content of butadiene structural units derived from butadiene in this copolymer is 85.6%, and the molar content of cis 1,4-structural units is 98.5%, based on the total amount of butadiene structural units. 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 96000, and the molecular weight distribution index (M w / M n ) is 1.7. Analysis by nuclear magnetic resonance spectroscopy shows that the molar content of butadiene structural units derived from butadiene in this copolymer is 82%, and the molar content of cis 1,4-structural units is 91.3%, based on the total amount of butadiene structural units. 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 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to another glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 0.8 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 60 minutes at 40°C. After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 8.70 g of copolymer. When measured by GPC analysis, this copolymer had a number average molecular weight (M n ) is 112000, and the molecular weight distribution index (M w / M n ) is 2.5. Analysis by nuclear magnetic resonance spectroscopy shows that the molar content of butadiene structural units derived from butadiene in this copolymer is 65.3%, and the molar content of cis 1,4-structural units is 88.4%, based on the total amount of butadiene structural units. 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 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to another glass bottle to obtain a triisobutylaluminum solution. 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were added in order to a 500 mL autoclave. Then, 0.8 MPa ethylene was introduced, and when it became saturated, the catalyst solution was added. Polymerization was performed for 60 minutes at 40°C. After the polymerization was completed, the product was poured into a large amount of hydrochloric acid-containing ethanol (2 wt ‰, hydrochloric acid is calculated as HCl) to precipitate, and the copolymer was separated by filtration and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining 4.81 g of copolymer. When measured by GPC analysis, 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 shows that the molar content of butadiene structural units derived from butadiene in this copolymer is 71.5%, and the molar content of cis 1,4-structural units is 86.3%, based on the total amount of butadiene structural units. 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 sufficient 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 the polymerization was completed, a small amount of hydrochloric acid-containing methanol was added to stop the reaction (2 wt %, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was separated and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining polybutadiene. As a result of calculation, the monomer conversion rate was 100%, and as measured by GPC analysis, 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 sufficient 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 the polymerization was completed, a small amount of hydrochloric acid-containing methanol was added to stop the reaction (2 wt ‰, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was separated and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining polybutadiene. As a result of calculation, the conversion rate of the monomer was 100%, 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 1.3. Nuclear magnetic resonance spectroscopy analysis 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 sufficient 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 the polymerization was completed, a small amount of hydrochloric acid-containing methanol was added to stop the reaction (2 wt ‰, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was separated and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining polybutadiene. The monomer conversion rate was 96.3%, and the number average molecular weight (M n ) is 125,000, and the molecular weight distribution index (M w / M n ) is 1.2. Nuclear magnetic resonance spectroscopy analysis 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 sufficient 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 the polymerization was completed, a small amount of hydrochloric acid-containing methanol was added to stop the reaction (2 wt %, hydrochloric acid is calculated as HCl). The product was poured into a large amount of ethanol, and the polymer was separated and washed with ethanol. It was dried in a vacuum oven until the weight did not decrease, thereby obtaining polybutadiene. As a result of calculation, the conversion rate of the monomer was 100%, and as measured by GPC analysis, 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 prove that the metallocene complex according to the present invention exhibits improved catalytic activity and can produce higher polymer yields. The metallocene complex according to the present invention can polymerize conjugated diolefins efficiently and region-selectively. When the metallocene complex according to the present invention is used in the copolymerization reaction of ethylene and conjugated diolefins, it can effectively copolymerize ethylene-conjugated diolefins and efficiently control the copolymerization 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 therefore can 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 scope of the technical idea of ​​the present invention, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in other suitable ways. These simple modifications and combinations are also considered as the disclosure content of this disclosure and are included in the protection scope of this 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 represents 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 represents hydrogen or C １ ~C ２０ is an alkyl group 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 C １ ~C ５ is an alkyl group 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 １ ~C ５ is an alkyl group of R ２ , R ４ , R ７ , and R ９ are each independently ６ ~C １２ R is an aryl of ３ , R ５ , R ８ , and R １０ are all hydrogen, Preferably, R １ , and R ６ is methyl, R ２ , R ４ , R ７ , and R ９ The metallocene complex of claim 1 , wherein is phenyl.

3. In formula I, R １ , R ４ , R ６ , and R ９ are each independently １ ~C ２０ is an alkyl group of R ２ , and R ７ are each independently ６ ~C ３０ R is an aryl of ３ , R ５ , R ８ , and R １０ are all hydrogen, Preferably, R １ , R ４ , R ６ , and R ９ are each independently １ ~C ５ is an alkyl group of R ２ , and R ７ are each independently ６ ~C １２ is an aryl of More preferably, R １ , R ４ , R ６ , and R ９ are each independently methyl or isopropyl; R ２ , and R ７ is phenyl, More preferably, R １ , and R ６ is methyl, R ４ , and R ９ is methyl or isopropyl, R ２ , and R ７ The metallocene complex of claim 1 , wherein is phenyl.

4. In formula I, R １ , R ４ , R ６ , and R ９ are each independently １ ~C ２０ is an alkyl group of R ２ , and R ７ are each independently ６ ~C ３０ R is an aryl of ５ , and R １０ are all hydrogen, R ３ , and R ８ Each independently represents -SiR ２３ R ２４ R ２５ and R ２３ , R ２４ , and R ２５ are the same or different, and each independently represents １ ~C ２０ is an alkyl group of Preferably, R １ , R ４ , R ６ , and R ９ are each independently １ ~C ５ is an alkyl group of R ２ , and R ７ are each independently ６ ~C １２ R is an aryl of ３ , and R ８ Each independently represents -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 C １ ~C ５ and R ２３ , R ２４ , and R ２５ At least one of １ ~C ５ is an alkyl group of More preferably, R １ , R ４ , R ６ , and R ９ is methyl, R ２ , and R ７ is phenyl, R ３ , and R ８ Each independently represents -SiR ２３ R ２４ R ２５ and R ２３ , R ２４ , and R ２５ The metallocene complex of claim 1 , wherein all of are methyl.

5. The metallocene complex according to any one of claims 1 to 4, wherein in formula I, Ln is scandium or gadolinium.

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

7. Step 1, contacting a precursor compound with a heterocyclic compound selected from the compounds represented by formula 2-2-1 and the compounds represented by formula 2-2-2 in the presence of an organolithium; Step 2 of contacting the mixture obtained in step 1 with an amine of 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; 【Chemistry 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 represents 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 represents hydrogen or C １ ~C ２０ is an alkyl group 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 represents hydrogen or C １ ~C ５ is an alkyl group of 2. The method for producing a metallocene complex according to claim 1, wherein M is an alkali metal atom, preferably potassium or sodium.

8. The mixture contacted in step 1 is used in step 2 without separation; Preferably, 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; 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 a second solvent; The method according to claim 7, 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.

9. 8. The method of claim 7, wherein in step 1, an organolithium is contacted with a heterocyclic compound of formula 2-2 to form a lithium salt, and the lithium salt is contacted with the precursor compound.

10. 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; 8. The method of claim 7, wherein in step 2, the contacting is carried out at a temperature of 0-30° C., and in step 2, the duration of the contacting is from 1 to 48 hours.

11. A catalyst composition comprising a metallocene complex and a cocatalyst, said metallocene complex being the metallocene complex according to any one of claims 1 to 6.

12. the co-catalyst is an organoaluminum compound and / or an organoboron compound; Preferably, the organoaluminum compound is an aluminoxane and / or a compound of formula V, The organoaluminum compound is preferably triisobutylaluminum and / or diisobutylaluminum hydride, Catalyst composition according to claim 11, wherein the organoboron compound is preferably an organoborate, preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethylium tetrakis(pentafluorophenyl)borate. 【Chemistry 5】 (In formula V, R １７ , R １８ , and R １９ are the same or different, and each independently represents hydrogen, C １ ~C １０ Alkyl, C １ ~C １０ Alkoxy, C ６ ~C ２０ Aryl of C ７ ~C １５ Alkalil, 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.)

13. the co-catalyst is an organoaluminum compound and an organoboron compound, the organoaluminum compound is preferably triisobutylaluminum and / or diisobutylaluminum hydride, and the organoboron compound is preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethylium tetrakis(pentafluorophenyl)borate; Preferably, in the co-catalyst, the molar ratio of the organoaluminum compound to the organoboron compound is 1:0.01-100, preferably 1:0.1-90, more preferably 1:0.5-60, the organoaluminum compound being calculated in terms of elemental aluminum, and the organoboron compound being calculated in terms of elemental boron; The catalyst composition according to claim 11, wherein the molar ratio of said metallocene complex to said organoboron cocatalyst is preferably 1:0.1-10, preferably 1:0.5-5.

14. A process for polymerizing olefins, comprising the step of contacting at least one olefin with components in a catalyst composition under olefin polymerization reaction conditions, said catalyst composition being the catalyst composition of any one of claims 11 to 13.

15. the olefin is a conjugated diolefin, or ethylene and a conjugated diolefin; 15. The method of claim 14, wherein the conjugated diolefin is preferably butadiene and / or isoprene.

16. An olefin polymer produced by the method according to claim 14 or 15.

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