Metallocene complexes and methods of making and catalyst compositions and uses thereof

Abstract

The present application relates to a kind of metallocene complex and its preparation method, catalyst composition and its use.The metallocene complex has the structure shown in formula I.Catalyst composition containing metallocene complex according to the present application shows improved catalytic activity, while also having higher structural regularity control ability of conjugated diene structural unit and higher ethylene and conjugated diene copolymerization capacity.Preparation process of metallocene complex according to the present application is simple, low cost.

Description

TECHNICAL FIELD

[0001] The present application relates to a metallocene complex and a method for preparing the same, and further relates to a catalyst composition containing the metallocene complex, and further relates to the use of the metallocene complex and the catalyst composition in olefin polymerization. BACKGROUND

[0002] Metallocene complexes are compounds in which a central metal is coordinated with one or more cyclopentadienyl groups or derivatives thereof, and play a very important role as catalysts in various polymerization reactions. Due to the difference in the type of ligand and central metal, metallocene complexes show different catalytic characteristics in polymerization reactions.

[0003] There have been many proposals for polymerization catalysts for conjugated diene polymerization. For example, it is known that high cis-1,4-conjugated diene polymers are obtained by using a complex catalyst system containing a neodymium compound and an organic aluminum compound as main components. Some of these polymers have been used industrially as a butadiene polymerization catalyst system. However, there has been a constant need for a method for efficiently producing conjugated diene polymers having a high content of cis-1,4-structure, a high molecular weight, and a narrow molecular weight distribution in the microstructure. Therefore, there is a need to develop a polymerization catalyst.

[0004] Ethylene is widely used in the plastics industry as a widely used and readily available monomer. Conjugated dienes, especially butadiene and isoprene, are the most important monomers for synthetic rubber. Butadiene, as a byproduct in the process of producing ethylene from a petroleum route, was once priced similarly to ethylene. Due to changes in the route of producing ethylene, resulting in a decrease in butadiene production, its price has risen sharply. In contrast, the price of ethylene has decreased. Therefore, it is very attractive to use ethylene as a raw material for producing rubber for tires, which can greatly save raw material costs. However, due to the difference in polymerization mechanism of conjugated dienes and α-olefins, it is difficult to copolymerize them. Therefore, it is a very challenging task to use the same catalytic system to catalyze the copolymerization of ethylene and conjugated dienes, and the copolymerization of the two has been the direction of efforts of academia and industry. It is very attractive to develop a metallocene complex that has high catalytic activity, high control ability of the structural regularity of conjugated diene structural units, and high copolymerization ability of ethylene and conjugated dienes.

[0005] In 2015, Michiue et al. reported a series of silicon-bridged disubstituted indenyl zirconium compounds for the preparation of ethylene / propylene copolymer with butadiene in the presence of hydrogen (K. Michiue, M. Mitani, T. Fujita, Catalysts 2015, 5, 2001-2017). The catalysts have high activity and can produce high molecular weight polymers. With the increase of steric hindrance of substituents on indene, the content of ethylene in the copolymer increases. However, the insertion rate of butadiene in the obtained copolymer is low, and the copolymer contains cyclopropyl and cyclopentyl structures. Rare earth catalysts have also been tried for the copolymerization of ethylene with conjugated dienes due to their good affinity for conjugated dienes. Boisson et al. reported a series of neodymium cyclopentadienyl catalysts that can efficiently catalyze the copolymerization of ethylene with 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 high, and mainly exists in the trans-1,4-structure. The molecular weight of the polymer is not high enough, and the polymer contains cyclohexyl structures.

[0006] Transition metal compounds with π ligands fused with heterocyclic five-membered rings and their use in the catalysis of the polymerization of monoolefins have been reported, which have the advantages of high activity and high molecular weight. However, there are few reports on the catalysis of ethylene-conjugated diene copolymerization. There are no reports on rare earth catalysts with fused heterocyclic five-membered rings and their use in the copolymerization of ethylene-conjugated dienes. SUMMARY

[0007] The purpose of the present application is to provide a catalyst composition with improved catalytic activity, which can accurately control the structure of conjugated diene structural units, thereby improving the structural regularity of conjugated diene structural units in the prepared polymer, and effectively regulating the copolymerization composition of the copolymer when used in the copolymerization of ethylene and conjugated dienes.

[0008] According to a first aspect of the present application, the present application provides a metallocene complex having the structure shown in formula I,

[0009]

[0010] In formula I, Ln is a lanthanide element, scandium or yttrium;

[0011] R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 identically or differently, each independently are hydrogen, C1-C 20 identically or differently, each independently are hydrogen, C1-C 30 identically or differently, each independently are hydrogen, C1-C 23 R 24 R 25 , R 23 , R 24 and R 25 identically or differently, each independently are hydrogen or C1-C 20 identically or differently, each independently are hydrogen or C1-C 11 , R 12 , R 13 , R 14 , R 15 and R 16 identically or differently, each independently are hydrogen or C1-C5alkyl; 17 identically or differently, each independently are hydrogen or C1-C5alkyl; 17 identically or differently, each independently are hydrogen or C1-C5alkyl; 12 identically or differently, each independently are hydrogen or C1-C5alkyl; 201 identically or differently, each independently are hydrogen or C1-C5alkyl; 202 identically or differently, each independently are hydrogen or C1-C5alkyl; E is O, S or N-R 203 , R 204 is C1-C5alkyl or C6-C 205 aryl. 20 30 According to a second aspect of the present application, the present application provides a method for preparing the metallocene complex of the first aspect of the present application, the method comprising the steps of: 23 24 Step 1, contacting a precursor compound with a heterocyclic compound in the presence of an organolithium, the heterocyclic compound being selected from the group consisting of a compound represented by Formula 2-2-1 and a compound represented by Formula 2-2-2, 25 23 Step 2, contacting the mixture obtained in Step 1 with an amine represented by Formula 2-3, 24 25 the precursor compound being a compound selected from the group consisting of a compound represented by Formula 2-1, 20 17 LnX (Formula 2-1) 17 12 in Formula 2-1, Ln is a lanthanide element, scandium or yttrium, 206 207 X is a halogen atom, preferably chlorine; 208 209 210 211 10 in Formula 2-2-1 and Formula 2-2-2, R 20 , R 30 , R 23 , R 24 and R 25 are the same or different, each independently are hydrogen, C1-CC6-Ci2-aryl or -SiR 30 C6-Ci2-aryl or -SiR 23 R 24 R 25 R 23 R 24 R 25 R 20 R

[0023] E is O, S or N-R 17 R 17 C6-Ci2-aryl or -SiR 12 C6-Ci2-aryl or -SiR

[0024]

[0025] R 206 R 207 R 208 R 209 R 210 R 211 R

[0026] M is an alkali metal atom, preferably potassium or sodium.

[0027] According to a third aspect of the present application, the present application provides a catalyst composition comprising a metallocene complex and a cocatalyst, wherein the metallocene complex is the metallocene complex according to the first aspect of the present application.

[0028] According to a fourth aspect of the present application, the present application provides the use of the metallocene complex according to the first aspect of the present application or the catalyst composition according to the third aspect of the present application as an olefin polymerization catalyst.

[0029] The catalyst composition comprising the metallocene complex according to the present application shows improved catalytic activity, and can effectively improve the yield of the polymer. Meanwhile, the metallocene complex according to the present application also has a higher control ability of the structural regularity of the conjugated diene structural unit and a higher copolymerization ability of ethylene and conjugated diene.

[0030] The catalyst composition comprising the metallocene complex according to the present application can accurately control the structure of the conjugated diene structural unit, thereby improving the structural regularity of the conjugated diene structural unit in the prepared polymer. The catalyst system comprising the metallocene complex according to the present application has good copolymerization performance, and can efficiently realize the copolymerization of ethylene and conjugated diene and effectively regulate the copolymerization composition of the copolymer.

[0031] The preparation method of the metallocene complex according to the present application prepares the metallocene complex by a "one-pot method", effectively simplifying the synthetic route, reducing the operation complexity and operation cost. DETAILED DESCRIPTION

[0032] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as exactly that endpoint. Any values that fall within common

[0033] According to a first aspect of the present application, the present application provides a metallocene complex, the complex having a structure shown in Formula I,

[0034]

[0035] In Formula I, Ln is a lanthanide element, scandium or yttrium.

[0036] In the present application, the term "lanthanide element" refers to a collective term of 15 elements from element No. 57 lanthanum to element No. 71 lutetium in the periodic table.

[0037] In Formula I, specific examples of Ln can 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).

[0038] Preferably, in Formula I, Ln is gadolinium or scandium. More preferably, in Formula I, Ln is gadolinium.

[0039] In Formula I, R1, R2, R3, R4, R5, R6, R7, R8, R9and R 10 are the same or different, each independently hydrogen, C1-C 20 alkyl, C6-C 30 aryl or -SiR 23 R 24 R 25 , R 23 , R 24 and R 25 are the same or different, each independently hydrogen or C1-C 20 alkyl; preferably, at least one of R 23 , R 24 and R 25 is C1-C 20 alkyl.

[0040] In this invention, C1-C 20 Alkyl groups include C1-C 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups and C3-C 20 Specific examples of cycloalkyl groups 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, hexadecyl and its various isomers, heptadecanyl and its various isomers, heptadecanyl and its various isomers, octadecyl and its various isomers, nonadecanyl and its various isomers, eicosyl and its various isomers, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0041] In this invention, C6-C 30 Specific examples of aryl groups may include, but are not limited to: phenyl, tolyl, ethylphenyl, propanylphenyl (wherein, the propyl group may be n-propyl or isopropyl), butylphenyl (wherein, the butyl group may be n-butyl, sec-butyl, isobutyl or tert-butyl), naphthyl, anthraceneyl or phenanthryl.

[0042] 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-C5 alkyl group. 12 Aryl groups, R3, R5, R8 and R 10 All are 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.

[0043] In another preferred embodiment, in formula I, R1, R4, R6, and R9 are each independently C1-C1. 20 The alkyl group, R2 and R7 are each independently C6-C. 30 Aryl groups, R3, R5, R8 and R 10 All are hydrogen. In this preferred embodiment, R1, R4, R6, and R9 are each independently preferably C1-C5 alkyl groups, and R2 and R7 are each independently preferably C6-C5 alkyl groups. 12 The aryl group. 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.

[0044] In another preferred embodiment, in formula I, R1, R4, R6and R9are each independently C1-C5alkyl, R2and R7are each independently C6-C10aryl, R5and R8are each hydrogen, and R3and R8are each independently -SiR 20 30 10 23 24 25 23 24 25 20 In this preferred embodiment, R1, R4, R6and R9are each independently preferably C1-C5alkyl, R2and R7are each independently preferably C6-C10aryl, R3and R8are each independently preferably -SiR 12 23 24 25 23 24 25 23 24 25 In this preferred embodiment, R1, R4, R6and R9are each independently more preferably methyl, R2and R7are each independently more preferably phenyl, R3and R8are each independently more preferably -SiR 23 24 25 23 24 25 In this preferred embodiment, Ln is preferably gadolinium.

[0045] In formula I, R 11 12 13 14 15 16 In formula I, R 11 12 13 14 15 16 In formula I, R 11 12 13 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​At least one of them is a C1-C5 alkyl group, R 14 R 15 and R 16 At least one of them is a C1-C5 alkyl group. More preferably, in formula I, R 11 R 12 R 13 R 14 R 15 and R 16 Whether the same or different, each is independently hydrogen or a C1-C5 alkyl group, and R 11 R 12 and R 13 At least two of them are C1-C5 alkyl groups, R 14 R 15 and R 16 At least two of them are C1-C5 alkyl groups. More preferably, in formula I, R... 11 R 12 R 13 R 14 R 15 and R 16 Whether identical or different, each is independently a C1-C5 alkyl group. More preferably, in formula I, R 11 R 12 R 13 R 14 R 15 and R 16 All are methyl groups.

[0046] In Equation I, E represents O, S, or NR. 17 R 17 It is a C1-C5 alkyl group or a C6-C alkyl group. 12 The aryl group. Preferably, in formula I, E is S.

[0047] According to the metallocene complexes of the present invention, the metallocene complexes are preferably those shown in Formula II, Formula III, Formula IV, or Formula V.

[0048]

[0049] According to the metallocene complexes of the present invention, the metallocene complexes are particularly preferred to be those shown in Formula II, Formula IV or Formula V.

[0050] According to a second aspect of the present invention, the present invention provides a method for preparing the metallocene complex described in the first aspect of the present invention, the method comprising the following steps:

[0051] Step 1, contacting a precursor compound with a heterocyclic compound in the presence of an organic lithium, the heterocyclic compound being selected from the group consisting of a compound represented by Formula 2-2-1 and a compound represented by Formula 2-2-2,

[0052] Step 2, contacting the mixture obtained in Step 1 with an amine represented by Formula 2-3,

[0053] the precursor compound being a compound selected from the group consisting of a compound represented by Formula 2-1,

[0054] LnX (Formula 2-1)

[0055] In Formula 2-1, Ln is a lanthanide element, scandium or yttrium, preferably gadolinium or scandium, more preferably gadolinium;

[0056] X is a halogen atom, for example, can be fluorine, chlorine, bromine or iodine, preferably chlorine;

[0057]

[0058] 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, each independently hydrogen, C1-C 20 alkyl, C6-C 30 aryl or -SiR 23 R 24 R 25 , R 23 , R 24 and R 25 are the same or different, each independently hydrogen or C1-C 20 alkyl;

[0059] In Formula 2-2-1 and Formula 2-2-2, E is O, S or N-R 17 , R 17 is C1-C5 alkyl, C6-C 12 aryl, preferably S;

[0060]

[0061] In Formula 2-3, R 206 , R 207 , R 208 , R 209 , R 210 and R 211 are the same or different, each independently hydrogen or C1-C5 alkyl,

[0062] M is an alkali metal atom, for example, can be lithium, sodium or potassium, preferably sodium or potassium, more preferably potassium.

[0063] According to the preparation method of the present application, the mixture obtained in step 1 is directly used as the raw material of step 2 without separation, and the separation operation of the mixture obtained in step 1 is omitted. The separation operation not only increases the complexity and cost of the operation, but also has an adverse effect on the yield of the target product due to the loss of materials during the separation process. According to the preparation method of the present application, the mixture obtained in step 1 is directly used in step 2 without separation, which not only simplifies the operation and reduces the cost, but also has no adverse effect on the yield of the target product.

[0064] According to the preparation method of the present application, in formula 2-2-1 and formula 2-2-2, R 201 , R 202 , R 203 , R 204 and R 205 correspond to R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 , respectively, in the compound of formula I, and their specific examples are subject to the compound of formula I, which will not be repeated here.

[0065] According to the preparation method of the present application, in formula 2-3, R 206 , R 207 , R 208 , R 209 , R 210 and R 211 correspond to R 11 , R 12 , R 13 , R 14 , R 15 and R 16 , respectively, in the compound of formula I, and their specific examples are subject to the compound of formula I, which will not be repeated here.

[0066] According to the preparation method of the present application, in step 1, the precursor compound is contacted with the heterocyclic compound in the presence of an organic lithium, which is preferably an organic monolithium compound, more preferably a compound of formula VII,

[0067] R 26 Li (formula VII)

[0068] In formula VII, R 26 is a C1-C 10alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl (including various isomers of hexyl), heptyl (including various isomers of heptyl), octyl (including various isomers of octyl), nonyl (including various isomers of nonyl), or decyl (including various isomers of decyl).

[0069] Specific examples of the organolithium can include, but are not limited to, one or two or more of ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, and isobutyl lithium.

[0070] Preferably, the organolithium is one or two or more selected from the group consisting of n-butyl lithium, sec-butyl lithium, isobutyl lithium, and t-butyl lithium. More preferably, the organolithium is n-butyl lithium.

[0071] In Step 1, the contact temperature of the precursor compound with the heterocyclic compound can be 0-65°C, and the duration of the contact can be 1-120 hours, preferably 1.2-80 hours, more preferably 1.5-40 hours, and further preferably 2-10 hours. In Step 1, the precursor compound is contacted with the heterocyclic compound lithium salt in a first solvent, and the first solvent is preferably one or two or more of tetrahydrofuran, diethyl ether, dioxane, and hexane. The precursor compound and the heterocyclic compound can be mixed with a portion of the first solvent to form a solution, and the solution containing the precursor compound can be mixed with the solution containing the heterocyclic compound, so that the precursor compound is contacted with the heterocyclic compound lithium salt to react.

[0072] In Step 1, the organolithium is preferably first contacted with the heterocyclic compound to form a lithium salt, and then contacted with the precursor compound, and the structure of the lithium salt is shown in Formulas 2-4.

[0073]

[0074] The heterocyclic compound can be dissolved in a first solvent and placed in an environment of -78°C to 0°C, and then an alkyl lithium is added to react. The temperature of the reaction of the heterocyclic compound with the alkyl lithium is preferably -78°C to 60°C, more preferably -50°C to 50°C, and further preferably -10°C to 30°C; and the time of the reaction is preferably 0.8-10h, more preferably 0.8-8h, and further preferably 1-5h.

[0075] According to the preparation method of the present application, the mixture formed by contacting the precursor compound with the heterocyclic compound in step 1 is not isolated, but directly contacted with the amine in step 2 to obtain the metallocene complex according to the present application. According to the preparation method of the present application, in step 2, the mixture obtained in step 1 is contacted with the amine, preferably in a second solvent, which is preferably one or more than one of toluene, xylene and chlorobenzene. Preferably, at least part of the first solvent in the mixture obtained by the contacting in step 1 is removed to obtain a mixture from which at least part of the first solvent is removed, and the mixture from which at least part of the first solvent is removed is mixed with the second solvent, so that the contacting in step 2 is carried out in the second solvent.

[0076] According to the preparation method of the present application, in step 2, the mixture obtained in step 1 can be contacted with the amine at a temperature of 0-30°C, and the duration of the contacting can be 1-48 hours.

[0077] According to the preparation method of the present application, the metallocene complex according to the present application can be separated from the mixture obtained in step 2 by using conventional methods. In a preferred embodiment, at least part of the second solvent in the reaction mixture obtained in step 2 can be removed, a third solvent is added to the reaction mixture from which at least part of the second solvent is removed, then solid-liquid separation is carried out, the liquid phase material is collected, the solvent of the liquid phase material is removed, and the residual solid phase material is the metallocene complex according to the present application. The third solvent can be one or more than one of hexane, heptane and toluene.

[0078] According to a third aspect of the present application, the present application provides a catalyst composition, which comprises a metallocene complex and a cocatalyst, wherein the metallocene complex is the metallocene complex according to the first aspect of the present application.

[0079] According to the catalyst composition of the present application, the cocatalyst can be a cocatalyst commonly used in the field of olefin polymerization. In a preferred embodiment, the cocatalyst is an organic aluminum compound and / or an organic boron compound.

[0080] The organic aluminum compound is preferably an aluminoxane and / or a compound represented by formula V,

[0081]

[0082] In formula V, R 17 , R 18 and R 19 are the same or different, and each is independently selected from hydrogen, C1-C 10 alkyl, C1-C 10 alkoxy, C6-C 20 aryl, C7-C 15 alkylaryl, C7-C15 Aryl groups and hydrogen atoms, and R 17 R 18 and R 19 They are not both hydrogen atoms.

[0083] The C1-C 10 Alkyl groups include C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups and C3-C 10 Specific examples of cycloalkyl groups 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.

[0084] The C1-C 10 Specific examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, propoxy, and butoxy.

[0085] The C6-C 20 Specific examples of aryl groups may include, but are not limited to: phenyl, tolyl, ethylphenyl, propanylphenyl (wherein, the propyl group may be n-propyl or isopropyl), butylphenyl (wherein, the butyl group may be n-butyl, sec-butyl, isobutyl or tert-butyl), naphthyl, anthraceneyl or phenanthryl.

[0086] The alkylaryl group refers to an aryl group having an alkyl substituent. Specific examples of the alkylaryl group may include, but are not limited to, tolyl, ethylphenyl, dimethylphenyl, and diethylphenyl.

[0087] The aralkyl group refers to an alkyl group having an aryl substituent. Specific examples of the aralkyl group may include, but are not limited to, benzyl, phenethyl, 1-phenylpropyl, 2-phenylpropyl, and 3-phenylpropyl.

[0088] Specific examples of the organoaluminum compound can include, but are not limited to, 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, ethyldialuminum hydride, butyldialuminum hydride, isobutyldialuminum hydride, octyldialuminum hydride, amyl- dialuminum hydride, diethylaluminum ethoxide, dipropylaluminum ethoxide, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, triamylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri(p-tolyl)aluminum, tribenzylaluminum, ethyldiphenylaluminum, ethyl(di-p-tolyl)aluminum, ethyl(dibenzyl)aluminum, diethylphenylaluminum, diethyl(p-tolyl)aluminum, and diethylbenzylaluminum.

[0089] In a preferred example, in formula V, R 17 , R 18 and R 19 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, and at most one of R 17 , R 18 and R 19 is hydrogen. More preferably, in formula V, R 17 , R 18 and R 19 are hydrogen or butyl, and at most one of R 17 , R 18 and R 19 is hydrogen.

[0090] According to the catalyst composition of the present application, the organoaluminum compound is preferably triisobutylaluminum and / or diisobutylaluminum hydride.

[0091] The organoboron compound is preferably an organoborate salt. The organoborate salt is an ionic compound consisting of a borate anion and a cation.

[0092] Specific examples of the borate anion can 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(methylphenyl)borate, tetra(dimethylphenyl)borate, (triphenyl-pentafluorophenyl)borate, [tris(pentafluorophenyl)phenyl]borate, and undeca-hydrido-7,8-dicarbaundecaborate.

[0093] Specific examples of the cation can include, but are not limited to, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, and ferrocenium cation containing transition metal. Among them, the carbonium cation includes tri-substituted carbonium cation such as triphenyl carbonium cation and tri(substituted phenyl) carbonium cation. More specific examples of the tri(substituted phenyl) carbonium cation include tri(tolyl) carbonium cation. Specific examples of the ammonium cation can include, but are not limited to, trialkylammonium cation such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N,N-dialkylbenzenaminium cation such as N,N-dimethylbenzenaminium cation, N,N-diethylbenzenaminium cation, and N,N-2,4,6-pentamethylbenzenaminium cation; and dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation. Specific examples of the phosphonium cation can include, but are not limited to, triarylphosphonium cation such as triphenylphosphonium cation, tri(tolyl)phosphonium cation, and tri(xylyl)phosphonium cation.

[0094] According to the catalyst composition of the present application, the organic boron compound is preferably N,N-dimethylbenzenaminium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl-tetrakis(pentafluorophenyl)borate.

[0095] According to the catalyst composition of the present application, the organic aluminum compound and the organic boron compound as the cocatalyst can be used alone or in combination.

[0096] In a preferred embodiment, the cocatalyst is an organic aluminum compound and an organic boron compound. In this preferred embodiment, the cocatalyst is more preferably triisobutylaluminum and N,N-dimethylbenzenaminium tetrakis(pentafluorophenyl)borate. In this preferred embodiment, the molar ratio of the organic aluminum compound to the organic boron compound in the cocatalyst can be 1:0.01-100, preferably 1:0.1-90, and more preferably 1:0.5-60, the organic aluminum compound being calculated as aluminum element, and the organic boron compound being calculated as boron element. In this preferred embodiment, the amount of the cocatalyst can be used conventionally. When the cocatalyst contains the organic boron compound, the molar ratio of the metallocene complex to the organic boron compound is preferably 1:0.1-10, and more preferably 1:0.5-5.

[0097] According to a fourth aspect of the present application, the present application provides the use of the metallocene complex according to the first aspect of the present application or the catalyst composition according to the third aspect of the present application as an olefin polymerization catalyst.

[0098] The metallocene complex and the catalyst composition according to the present application are particularly suitable for use in the copolymerization of ethylene and a conjugated diene. In a preferred embodiment, the olefin is a conjugated diene. In another preferred embodiment, the olefin is ethylene and a conjugated diene.

[0099] The conjugated diene refers to a compound having a conjugated double bond in the molecular structure. The conjugated diene can be one or two or more selected from the group consisting of compounds represented by Formula VI,

[0100]

[0101] In Formula VI, R 20 , R 21 and R 22 are the same or different, and each is selected from the group consisting of hydrogen and a C1-C5 linear or branched alkyl group.

[0102] Specific examples of the conjugated diene can include, but are not limited to, butadiene and / or isoprene. Preferably, the conjugated diene is butadiene.

[0103] As a preferred example, the olefin is ethylene and butadiene, and ethylene and butadiene are contacted with the catalyst composition of the present application to obtain an ethylene-butadiene copolymer. The ethylene-butadiene copolymer contains ethylene structural units derived from ethylene and conjugated diene structural units derived from the conjugated diene. In this preferred example, the content of the ethylene structural units can be 80 mol% or less, preferably 5-70 mol%, and more preferably 10-60 mol%, based on the total amount of the ethylene-butadiene copolymer. In this preferred embodiment, the content of cis 1,4-structural units among the structural units derived from the conjugated diene is preferably 85 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and more further preferably 98 mol% or more. In this preferred example, the conjugated diene is preferably butadiene.

[0104] In the present application, the cis structural unit refers to a structural unit having a cis configuration among the conjugated diene structural units, and the cis 1,4-structural unit refers to a structural unit formed by 1,4-polymerization of the conjugated diene and having a cis configuration.

[0105] In this preferred example, the amount of the metallocene complex in the catalyst composition is preferably 0.1-1000 μmol per 1 mol of the conjugated diene.

[0106] When the metallocene complexes or catalyst compositions of the present invention are used for olefin polymerization, the polymerization can be carried out at a temperature of -100°C to 150°C, preferably at a temperature of 10-50°C. The polymerization can be performed using polymerization methods commonly used in the art; in a preferred embodiment, polymerization is carried out in solution.

[0107] The present invention will be described in detail below with reference to embodiments, but this does not limit the scope of the invention.

[0108] In the following examples and comparative examples, the molecular weight and molecular weight distribution index (M) of the polymers are... w / M n The assay was performed using an Agilent Technologies 1260 Infinity II high-temperature gel permeation chromatograph, employing two MIXD-B columns (300 × 7.5 mm) and one Guard column (50 × 7.5 mm). The mobile phase was trichlorobenzene, with a flow rate of 1 mL / min; the sample concentration was 1 mg / mL, and the injection volume was 200 μL; the test temperature was 150 °C; and monodistributed polystyrene was used as the standard sample.

[0109] In the following examples and comparative examples, nuclear magnetic resonance (NMR) spectroscopy was performed using a commercially available 400MHz NMR spectrometer from Bruker. Polybutadiene was tested at room temperature with deuterated chloroform as the solvent and tetramethylsilane (TMS) as the internal standard. Ethylene-butadiene copolymer was tested at 100°C with deuterated tetrachloroethane as the solvent. The content of cis-1,4 structural units in the butadiene structural units was determined based on the polymer... 13 Calculations from the C NMR spectrum showed that the peak at 26.5–27.5 ppm corresponded to carbon atoms in the cis-1,4 structural unit, while the peaks at 26.5–27.5 ppm and 31.5–32.5 ppm corresponded to carbon atoms in the butadiene structural unit; the content of ethylene structural units in the copolymer was determined according to… 13 Calculations from the C10 NMR spectra showed that the peaks at 28.5–30.0 ppm corresponded to carbon atoms in the ethylene structural unit, while the peaks at 26.5–27.5 ppm and 31.5–32.5 ppm corresponded to carbon atoms in the butadiene structural unit. Here, 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 formed by 1,4-polymerization of butadiene with a cis configuration.

[0110] In the following examples and comparative examples, the formula for calculating the monomer conversion rate is as follows:

[0111] Monomer conversion rate (%) = mass of polymer obtained / mass of added monomer × 100%.

[0112] Preparation Examples 1-4 are used to prepare metallocene complexes according to the present invention.

[0113] Preparation Example 1

[0114] Synthesis of bis(2-methyl-3,5-diphenyl-6-hydro-cyclopentathiophene) gadolinium bis(trimethylsilylamide) (complex shown in Formula II)

[0115]

[0116] To a solution of 40 mL of GdCl3(0.791 g, 3 mmol) in THF, 20 mL of a solution of 2-methyl-3,5-diphenyl-6-hydro-cyclopentathiophene and lithium salt synthesized from n-butyllithium (1.819 g, 6.2 mmol) in THF was slowly added under a nitrogen atmosphere. Then, the mixture was stirred at a temperature of 65 °C for 6 hours. Thereafter, THF was evaporated under reduced pressure, and 50 mL of toluene was added. Then, 20 mL of a solution of KN(SiMe3)2(0.519 g, 2.6 mmol) in toluene was slowly added to the mixture, followed by stirring 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 filtered off. Thereafter, hexane was evaporated under reduced pressure to obtain the target product as a light yellow solid (1.336 g, yield 50%). The product was analyzed using elemental analysis, and the elemental analysis results were C 61.91; H 5.42.

[0117] Preparation Example 2

[0118] Synthesis of bis(2,5-dimethyl-3-phenyl-6-hydro-cyclopentathiophene) scandium bis(dimethylsilylamide) (complex shown in Formula III)

[0119]

[0120] A metallocene complex was prepared in the same manner as in Preparation Example 1, except that ScCl3was used instead of GdCl3in Preparation Example 1, 2,5-dimethyl-3-phenyl-6-hydro-cyclopentathiophene was used instead of 2-methyl-3,5-diphenyl-6-hydro-cyclopentathiophene, and KN(SiMe2H)2was used instead of KN(SiMe3)2, to obtain the target product as a light yellow solid (1.183 g, yield 63%). The product was analyzed using elemental analysis, and the elemental analysis results were C 65.91; H 6.76.

[0121] Preparation Example 3

[0122] Synthesis of bis(2-methyl-3-phenyl-5-isopropyl-6-hydro-cyclopentathiophene) gadolinium bis(trimethylsilylamide) (complex shown in Formula IV)

[0123]

[0124] The same method as in Preparation Example 1 was used to prepare the metallocene complex, except that 2-methyl-3-phenyl-5-isopropyl-6-hydro-cyclopentathiophene was used instead of 2-methyl-3,5-diphenyl-6-hydro-cyclopentathiophene in Preparation Example 1, to obtain the target product as a white solid (1.357 g, yield 55%). The product was analyzed by elemental analysis, and the elemental analysis results were: C 58.28; H 6.36.

[0125] Preparation Example 4

[0126] Synthesis of Bis(2,5-dimethyl-3-phenyl-4-trimethylsilyl-6-hydro-cyclopentathiophene) gadolinium bis(trimethylsilyl amide) (complex shown in Formula V)

[0127]

[0128] The same method as in Preparation Example 1 was used to prepare the metallocene complex, except that 2,5-dimethyl-3-phenyl-4-trimethylsilyl-6-hydro-cyclopentathiophene was used instead of 2-methyl-3,5-diphenyl-6-hydro-cyclopentathiophene in Preparation Example 1, to obtain the target product as a white solid (1.232 g, yield 45%). The product was analyzed by elemental analysis, and the elemental analysis results were: C 55.27; H 6.63.

[0129] Preparation Comparative Example 1

[0130] The complex VI was synthesized according to the method described in the literature Dalton Trans., 2008, 2531-2533.

[0131]

[0132] Examples 1-8 serve to illustrate the catalyst composition and use according to the application.

[0133] Example 1

[0134] In a glove box under argon atmosphere, 4.46 mg of the complex shown in 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 1 M triisobutylaluminum hexane solution was added. After being dissolved thoroughly, 3.5 mL of a toluene solution of butadiene (containing butadiene 0.54 g) 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 terminate the reaction. The product was poured into a large amount of ethanol to separate the polymer, which was washed with ethanol. Drying was carried out in a vacuum oven until the weight no longer decreased, thereby obtaining polybutadiene. The monomer conversion was determined to be 100% by calculation, and the number average molecular weight (M n ) of the polymer was determined to be 112000 by GPC analysis, and the molecular weight distribution index (M w / M n ) was 1.2.

[0135] The obtained polybutadiene was analyzed by nuclear magnetic resonance spectroscopy, and it was determined that the molar content of cis-1,4-structural units in the polybutadiene was greater than 99%.

[0136] Example 2

[0137] In a glove box under argon atmosphere, 30.34 mg of the complex shown in formula II and 27.24 mg of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were dissolved in 8 mL of toluene to obtain a catalyst solution. In another glass bottle, 2 mL of 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to obtain a triisobutylaluminum solution.

[0138] In a 500 mL autoclave, 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was carried out at 40°C for 60 minutes. After the polymerization was completed, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, calculated as HCl), precipitated, and the copolymer was separated by filtration and washed with ethanol. Drying was carried out in a vacuum oven until the weight no longer decreased, thereby obtaining 14.6 g of the copolymer. The number average molecular weight (M n ) of the copolymer was determined to be 105000 by GPC analysis, and the molecular weight distribution index (M w / M n ) was 1.6.

[0139] The obtained polymer was analyzed by nuclear magnetic resonance spectroscopy, and it was determined that the molar content of butadiene structural units derived from butadiene in the prepared polymer was 86.2%; and the molar content of cis-1,4-structural units was 95.2% based on the total amount of butadiene structural units.

[0140] Example 3

[0141] In a glove box under argon atmosphere, 28.03 mg of the complex represented by formula III and 31.36 mg of triphenylmethyl-tetra(pentafluorophenyl)borate were dissolved in 8 mL of toluene in a glass bottle to obtain a catalyst solution. In another glass bottle, 2 mL of 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to obtain a triisobutylaluminum solution.

[0142] In a 500 mL autoclave, 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was carried out at room temperature (25°C) for 180 minutes. After the completion of polymerization, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, based on HCl), precipitated, and filtered to separate the copolymer, which was washed with ethanol. Drying in a vacuum oven until the weight no longer decreased resulted in 13.2 g of the copolymer, which was analyzed by GPC to determine that the number average molecular weight (Mn) of the copolymer was 131,000, and the molecular weight distribution index (Mw / Mn) was 3.7. n w n

[0143] NMR spectroscopy analysis confirmed that the molar content of butadiene structural units derived from butadiene in the prepared polymer was 65.2%, and the molar content of cis-1,4-structural units was 90.5% based on the total amount of butadiene structural units.

[0144] Example 4

[0145] In a glove box under argon atmosphere, 4.12 mg of the complex represented by formula IV and 4.00 mg of N,N-dimethylanilinium tetra(pentafluorophenyl)borate were dissolved in 3.6 mL of toluene in a glass bottle, and 0.1 mL of 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 the completion of polymerization, a small amount of methanol containing hydrochloric acid was added to terminate the reaction (2 wt%, based on HCl). The product was poured into a large amount of ethanol to separate the polymer, which was washed with ethanol. Drying in a vacuum oven until the weight no longer decreased resulted in polybutadiene, and calculation determined that the monomer conversion was 100%, and GPC analysis determined that the number average molecular weight (Mn) of the polymer was 101,000, and the molecular weight distribution index (Mw / Mn) was 1.4. n w n

[0146] NMR spectroscopy analysis confirmed that the molar content of cis-1,4-structural units in the obtained polybutadiene was greater than 99%.

[0147] Example 5 ​​​​​​

[0148] In a glove box under 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. In another glass bottle, 2 mL of 1 M diisobutylaluminum hydride hexane solution and 7 mL of toluene were added to obtain a diisobutylaluminum hydride solution.

[0149] In a 500 mL autoclave, 120 g of toluene, the diisobutylaluminum hydride solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was performed at room temperature (25°C) for 180 minutes. After completion of the polymerization, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, based on HCl), precipitated, and the copolymer was separated by filtration and washed with ethanol. Drying was performed in a vacuum oven until the weight no longer decreased, whereby 12.1 g of the copolymer was obtained. The number average molecular weight (Mn) of the copolymer was 288,000, and the molecular weight distribution index (Mw / Mn) was 2.4, as determined by GPC analysis. n w n

[0150] Analysis by nuclear magnetic resonance spectroscopy revealed that the molar content of butadiene structural units derived from butadiene in the copolymer was 78.3%, and the molar content of cis-1,4-structural units was greater than 99% based on the total amount of butadiene structural units.

[0151] Example 6

[0152] In a glove box under 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. In another glass bottle, 2 mL of 1 M diisobutylaluminum hydride hexane solution and 7 mL of toluene were added to obtain a diisobutylaluminum hydride solution.

[0153] In a 500 mL autoclave, 120 g of toluene, the diisobutylaluminum hydride solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was performed at room temperature (25°C) for 180 minutes. After completion of the polymerization, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, based on HCl), precipitated, and the copolymer was separated by filtration and washed with ethanol. Drying was performed in a vacuum oven until the weight no longer decreased, whereby 12.1 g of the copolymer was obtained. The number average molecular weight (Mn) of the copolymer was 288,000, and the molecular weight distribution index (Mw / Mn) was 2.4, as determined by GPC analysis. n w n

[0154] ​​​​​​The copolymer prepared was analyzed by nuclear magnetic resonance spectroscopy to determine that the copolymer contained 48.4% by mole of butadiene structural units derived from butadiene; and that the copolymer contained 90.2% by mole of cis-1,4- structural units based on the total amount of butadiene structural units.

[0155] Example 7

[0156] In a glove box under an argon atmosphere, 30.34 mg of the complex of 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. In another glass bottle, 2 mL of a 1 M solution of triisobutylaluminum in hexane and 7 mL of toluene were added to obtain a triisobutylaluminum solution.

[0157] In a 500 mL autoclave, 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was performed at room temperature (25°C) for 180 minutes. After the polymerization was completed, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, based on HCl), precipitated, and filtered to separate the copolymer, which was then washed with ethanol. The copolymer was dried in a vacuum oven until the weight no longer decreased, thereby obtaining 5.14 g of the copolymer. The number average molecular weight (Mn) of the copolymer was 83,000, and the molecular weight distribution index (Mw / Mn) was 2.7, as determined by GPC analysis. n w n

[0158] The copolymer prepared was analyzed by nuclear magnetic resonance spectroscopy to determine that the copolymer contained 48.4% by mole of butadiene structural units derived from butadiene; and that the copolymer contained 90.2% by mole of cis-1,4- structural units based on the total amount of butadiene structural units.

[0159] Comparative Example 1

[0160] The same method as in Example 2 was used, except that the metallocene complex VI prepared in Comparative Example 1 was used instead of the complex of Formula II, to obtain 13.8 g of a copolymer. The number average molecular weight (Mn) of the copolymer was 96,000, and the molecular weight distribution index (Mw / Mn) was 1.7, as determined by GPC analysis. n w n

[0161] The copolymer prepared was analyzed by nuclear magnetic resonance spectroscopy to determine that the copolymer contained 48.4% by mole of butadiene structural units derived from butadiene; and that the copolymer contained 90.2% by mole of cis-1,4- structural units based on the total amount of butadiene structural units.

[0162] Example 8 ​​​​​​

[0163] In a glove box under argon atmosphere, 22.24 mg of the complex represented by the following 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. In another glass bottle, 2 mL of 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to obtain a triisobutylaluminum solution.

[0164] In a 500 mL autoclave, 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was performed at 40°C for 60 minutes. After completion of the polymerization, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, based on HCl), precipitated, and the copolymer was separated by filtration and washed with ethanol. Drying was performed in a vacuum oven until the weight no longer decreased, whereby 8.70 g of the copolymer was obtained. The number average molecular weight (Mn) of the copolymer was 112,000, and the molecular weight distribution index (Mw / Mn) was 2.5, as determined by GPC analysis. n w n

[0165] NMR spectroscopy analysis confirmed that the molar content of butadiene structural units derived from butadiene in the prepared polymer was 65.3%, and the molar content of cis-1,4-structural units was 88.4% based on the total amount of butadiene structural units.

[0166] Comparative Example 2

[0167] This comparative example used a complex represented by the following formula VII:

[0168]

[0169] In a glove box under argon atmosphere, 22.24 mg of the complex represented by the following 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. In another glass bottle, 2 mL of 1 M triisobutylaluminum hexane solution and 7 mL of toluene were added to obtain a triisobutylaluminum solution.

[0170] In a 500 mL autoclave, 120 g of toluene, the triisobutylaluminum solution, and 14 g of butadiene were sequentially added. Then, 0.8 MPa of ethylene was introduced, and after saturation, the catalyst solution was added. Polymerization was performed at 40°C for 60 minutes. After completion of the polymerization, the product was poured into a large amount of ethanol to which hydrochloric acid had been added (2 wt%, based on HCl), precipitated, and the copolymer was separated by filtration and washed with ethanol. Drying was performed in a vacuum oven until the weight no longer decreased, whereby 8.70 g of the copolymer was obtained. The number average molecular weight (Mn) of the copolymer was 112,000, and the molecular weight distribution index (Mw / Mn) was 2.5, as determined by GPC analysis. n ​​​) is 105000, the molecular weight distribution index (M w / M n ) is 2.3.

[0171] The butadiene structural units derived from butadiene in the prepared polymer were determined by nuclear magnetic resonance spectroscopy analysis to be 71.5% in mole content; the mole content of cis-1,4-structural units was 86.3% based on the total amount of butadiene structural units.

[0172] The experimental results of Examples 1-8 demonstrate that the metallocene complex according to the present application exhibits improved catalytic activity and higher polymer yield can be obtained. The metallocene complex according to the present application can efficiently and highly regioselectively polymerize conjugated dienes. When the metallocene complex according to the present application is used in the copolymerization reaction of ethylene and conjugated dienes, the copolymerization of ethylene-conjugated dienes can be efficiently carried out and the copolymerization composition of the copolymer can be effectively controlled.

[0173] Comparing Example 2 with Comparative Example 1 and Example 8 with Comparative Example 2 shows that under the same conditions, the polymerization method of the present application can produce more copolymer, indicating that the transition metal complex used in the polymerization method of the present application has higher catalytic activity, thereby achieving higher polymerization efficiency.

[0174] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application and fall within the protection scope of the present application.

Claims

1. A metallocene complex having a structure represented by Formula I, in Formula I, Ln is scandium or gadolinium; R2and R7are each independently C6-C10aryl; and 30 C6-C10aryl; and R4and R9are each independently C1-C 20 alkyl or C6-C 30 aryl; R1, R3, R5, R6, R8and R 10 are identical or different, each independently hydrogen, C1-C 20 alkyl or -SiR 23 R 24 R 25 , R 23 , R 24 and R 25 are identical or different, each independently hydrogen or C1-C 20 alkyl, and at least one of R 23 , R 24 and R 25 is C1-C 20 alkyl; R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are the same or different, each independently hydrogen or C1-C5alkyl, and at least one of R 11 , R 12 and R 13 is C1-C5alkyl, at least one of R 14 , R 15 and R 16 is C1-C5alkyl; E is O or S.

2. The metallocene complex of claim 1, wherein, In formula I, R1and R6are each independently C1-C5alkyl, R2, R4, R7and R9are each independently C6-C10aryl, R3, R5, R8and R 12 are each hydrogen. 10 are each hydrogen.

3. The metallocene complex of claim 2, wherein, in Formula I, R1 and R6 are methyl, and R2, R4, R7 and R9 are phenyl.

4. The metallocene complex of claim 1, wherein, In formula I, R1, R4, R6and R9are each independently C1-C 20 alkyl, R2and R7are each independently C6-C 30 aryl, R3, R5, R8and R 10 are each hydrogen.

5. The metallocene complex of claim 4, wherein, In formula I, R1, R4, R6, and R9 are each independently C1-C5 alkyl, R2 and R7 are each independently C6-C 12 aryl.

6. The metallocene complex of claim 4, wherein, in Formula I, R1, R4, R6 and R9 are each independently methyl or isopropyl, and R2 and R7 are phenyl.

7. The metallocene complex of claim 4, wherein, in Formula I, R1 and R6 are methyl, and R4 and R9 are methyl or isopropyl, and R2 and R7 are phenyl.

8. The metallocene complex of claim 1, wherein, In formula I, R1, R4, R6 and R9 are each independently C1-C 20 alkyl, R2 and R7 are each independently C6-C 30 aryl, R5 and R 10 are each hydrogen, R3 and R8 are each independently -SiR 23 R 24 R 25 , R 23 , R 24 and R 25 are the same or different, each independently C1-C 20 alkyl, and at least one of R 23 , R 24 and R 25 is C1-C 20 alkyl.

9. The metallocene complex of claim 8, wherein, In Formula I, R1, R4, R6, and R9 are each independently a C1-C5 alkyl group, and R2 and R7 are each independently a C6-C5 alkyl group. 12 The aryl group, R3 and R8, are each independently -SiR 23 R 24 R 25 R 23 R 24 and R 25 Whether the groups are the same or different, each is independently hydrogen or a C1-C5 alkyl group, and R 23 R 24 and R 25 At least one of them is a C1-C5 alkyl group.

10. The metallocene complex of claim 9, wherein, In formula I, R1, R4, R6and R9are methyl, R2and R7are phenyl, R3and R8are each independently -SiR 23 R 24 R 25 , R 23 , R 24 and R 25 are each methyl.

11. The metallocene complex of claim 1, wherein, the metallocene complex is a complex represented by Formula II, Formula III, Formula IV, or Formula V, 12. A method for producing the metallocene complex according to claim 1, the method comprising the steps of: Step 1, contacting a precursor compound with a heterocyclic compound selected from the group consisting of a compound represented by Formula 2-2-1 and a 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 a compound selected from the group consisting of a compound represented by Formula 2-1, LnX (Formula 2-1) in Formula 2-1, Ln is scandium or gadolinium, X is a halogen atom; In formulae 2-2-1 and 2-2-2, R 202 is C6-C 30 aryl, R 204 is C1-C 20 alkyl or C6-C 30 aryl, R 201 , R 203 and R 205 are identical or different and each independently hydrogen, C1-C 20 alkyl or -SiR 23 R 24 R 25 , R 23 , R 24 and R 25 are identical or different and each independently hydrogen or C1-C 20 alkyl, and at least one of R 23 , R 24 and R 25 is C1-C 20 alkyl; in Formula 2-2-1 and Formula 2-2-2, E is O or S; In formula 2-3, R 206 , R 207 , R 208 , R 209 , R 210 , and R 211 are the same or different, each independently hydrogen or C1-C5 alkyl, and at least one of R 206 , R 207 , and R 208 is C1-C5 alkyl, at least one of R 209 , R 210 , and R 211 is C1-C5 alkyl. M is an alkali metal atom.

13. The method of claim 12, wherein, in Formula 2-1, X is chlorine.

14. The method of claim 12 or 13, wherein, in Formula 2-3, M is potassium or sodium.

15. The method of claim 12, wherein, The mixture obtained by the contacting in Step 1 is used in Step 2 without isolation.

16. The method of claim 12, wherein, 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, the method comprising removing at least part of the first solvent from the mixture obtained by the contacting in Step 1 to obtain a mixture from which at least part of the first solvent is removed, and mixing the mixture from which at least part of the first solvent is removed with the second solvent.

17. The method of claim 16, wherein, the first solvent is one or two or more selected from the group consisting of tetrahydrofuran, diethyl ether, dioxane and hexane, and the second solvent is one or two or more selected from the group consisting of toluene, xylene and chlorobenzene.

18. The method of claim 12, wherein, in Step 1, the organolithium is contacted with the heterocyclic compound selected from the group consisting of a compound represented by Formula 2-2-1 and a compound represented by Formula 2-2-2 to form a lithium salt, and the lithium salt is contacted with the precursor compound.

19. The method of claim 12, wherein, the contacting in Step 1 is carried out at a temperature of 0 to 65°C, and the contacting in Step 1 is carried out for a period of 1 to 120 hours; the contacting in Step 2 is carried out at a temperature of 0 to 30°C, and the contacting in Step 2 is carried out for a period of 1 to 48 hours.

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

21. The catalyst composition of claim 20, wherein, the cocatalyst is an organoaluminum compound and / or an organoboron compound.

22. The catalyst composition of claim 21, wherein, the organoaluminum compound is aluminoxane and / or a compound represented by Formula V, In formula V, R 17 R 18 and R 19 Whether the two are the same or different, they are each independently selected from hydrogen, C1-C 10 Alkyl, C1-C 10 alkoxy groups, C6-C 20 aryl, C7-C 15 alkylaryl, C7-C 15 Aryl groups and hydrogen atoms, and R 17 R 18 and R 19 They are not both hydrogen atoms.

23. The catalyst composition of claim 21, wherein, the organoaluminum compound is triisobutylaluminum and / or diisobutylaluminum hydride.

24. The catalyst composition of claim 21, wherein, the organoboron compound is an organoborate.

25. The catalyst composition of claim 21, wherein, the organoboron compound is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl-tetrakis(pentafluorophenyl)borate.

26. The catalyst composition of claim 20, wherein, the cocatalyst is an organoaluminum compound and an organoboron compound.

27. The catalyst composition of claim 26, wherein, The organic aluminum compound is triisobutylaluminum and / or diisobutylaluminum hydride, and the organic boron compound is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl-tetrakis(pentafluorophenyl)borate.

28. The catalyst composition of claim 26 or 27, wherein, In the cocatalyst, the molar ratio of the organic aluminum compound to the organic boron compound is 1:0.01-100, the organic aluminum compound being calculated as aluminum element, and the organic boron compound being calculated as boron element.

29. The catalyst composition of claim 26 or 27, wherein, In the cocatalyst, the molar ratio of the organic aluminum compound to the organic boron compound is 1:0.1-90, the organic aluminum compound being calculated as aluminum element, and the organic boron compound being calculated as boron element.

30. The catalyst composition of claim 26 or 27, wherein, In the cocatalyst, the molar ratio of the organic aluminum compound to the organic boron compound is 1:0.5-60, the organic aluminum compound being calculated as aluminum element, and the organic boron compound being calculated as boron element.

31. The catalyst composition of claim 26 or 27, wherein, In the cocatalyst, the molar ratio of the metallocene complex to the organic boron compound is 1:0.1-10.

32. The catalyst composition of claim 26 or 27, wherein, In the cocatalyst, the molar ratio of the metallocene complex to the organic boron compound is 1:0.5-5.

33. Use of the metallocene complex according to any one of claims 1-11 or the catalyst composition according to any one of claims 20-32 as an olefin polymerization catalyst.

34. The use of claim 33, wherein, The olefin is a conjugated diene, or the olefin is ethylene and a conjugated diene.

35. The use of claim 34, wherein, The conjugated diene is butadiene and / or isoprene. The conjugated diene is butadiene and / or isoprene.

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