Metal complex, preparation method and application thereof, and preparation method of olefin copolymer

Abstract

The invention relates to the technical field of materials and chemical engineering, and discloses a metal complex, a preparation method and application thereof, and a preparation method of an olefin copolymer. The metal complex has a structure as shown in a formula (I), R has a structure as shown in a formula (II), when the metal complex is adopted to catalyze olefin copolymerization, the activity is high, and preparation raw materials of a catalyst are low in price and low in toxicity, so that industrial application is facilitated. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of materials and chemical engineering, and in particular to a metal complex and a preparation method and application thereof, as well as a preparation method of an olefin copolymer. Background Art

[0002] Under high temperature and high pressure conditions, copolymers of ethylene and vinyl monomers containing polar groups (acrylates, vinyl acetate, etc.) with many branches, low crystallinity and low mechanical properties can be obtained by free radical polymerization. In addition, by using a suitable catalyst, harsh reaction conditions can be reduced, while reducing polymer branches, improving their crystallinity and mechanical properties. The use of late transition metals to prepare coordination compounds as catalysts is a method that has attracted widespread attention. The activity of such catalysts is largely determined by the ligand structure. In addition, metal Pd is rare and precious, which greatly increases the cost of catalyst preparation, making it difficult for Pd-based catalysts to be promoted to industrial applications.

[0003] The SHOP (Shell Higher Olefins Process) catalyst developed by Shell uses a PO-type ligand and a divalent nickel ion to form a neutral complex catalyst. When used for copolymerization of polar monomers, it can only catalyze monomers whose polar groups are far away from the double bonds, resulting in limited application range.

[0004] The diimine ligand palladium complex catalyst disclosed in USP4698403 can produce ethylene / acrylate copolymers with rich branch structures. 3 -Allyl-Palladium(II) Complexes" (GM Direnzo et al., J Am Chem Soc, 1996, 118, 6225) and "Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and α-Olefins with Methyl Acrylate" (S. Mecking et al., J Am Chem Soc, 1998, 120, 888) disclose diimine cationic catalysts (mainly iron and cobalt ions) which can be used for the copolymerization of ethylene and methyl methacrylate under the condition of methylaluminoxane as a cocatalyst. Polymers with more branches can also be obtained, but the polar monomers are only present at the ends of the polymers rather than in the main chain. Such multi-branched copolymers are all low in crystallinity.

[0005] "Funtionalised polyolefin synthesis using [P,O]Ni catalysts" (VC Gibson et al., Chem Commun, 2001, 1964), "Late-Metal Catalysts for Ethylene Homo-and Copolymerization" (SD Ittelet et al., Chem Rev, 2000, 100, 1169) and "Palladium catalysed copolymerization of ethene with alkylacrylates: polar comonomer built into the linear polymer chain" (E. Drent et al., Chem Commun, 2002, 744) disclose palladium complex catalysts with phosphine sulfonic acid ligand structures, which can be used for copolymerization of ethylene with various polar monomers. However, as mentioned above, the metal palladium used in such catalysts is extremely expensive and difficult to promote to industrial applications.

[0006] CN102197040A uses diphenylphosphine to replace phenol as the core ligand structure, and preferably nickel as the central metal to prepare a catalyst that can be used to synthesize α-olefin / (meth)acrylate. The resulting copolymer has few molecular branches and high molecular weight; however, even in the optimal case, the catalyst copolymerization activity is still low, and the main ligand raw material is phenol, which has acute toxicity.

[0007] CN106632507A uses diphenylphosphine to replace indole as the core ligand structure, preferably nickel as the central metal, to prepare a catalyst that can be used for copolymerization of α-olefins with one or more polar monomers such as acrylate, methacrylate, acrylic acid, unsaturated carboxylic acid ester, acrylamide, olefin nitrile, enol, olefin ether, etc. The binary copolymer has the characteristics of less molecular branching and high molecular weight. However, there is still a problem of low catalyst copolymerization activity. Similarly, the main ligand synthesis raw material is indole with acute toxicity.

[0008] CN109320558A uses a naphthol skeleton as the core ligand structure and nickel as the central metal to prepare polar monomers that can be used for ethylene and acrylates. The copolymerization activity is improved; the defects of this technology or the shortcomings of the present invention: the copolymerization activity of the catalyst in the optimal embodiment still has room for further improvement. However, the catalyst described therein is only suitable for homopolymerization or copolymerization of ethylene, and the application range is relatively small. The main ligand raw materials are pyridine, naphthol, etc. with high toxicity, and the toxicity problem has not been overcome.

[0009] Although the performance of current catalysts has been improved, the copolymerization activity of the catalysts is still significantly lower than that of Ziegler-Natta catalysts or even compared with homopolymerization, and the toxicity problem still exists in the preparation of catalysts. From the perspective of industrial application, efforts should continue to be made to develop and improve the copolymerization activity of such catalysts. Summary of the invention

[0010] The purpose of the present invention is to overcome the problems that the catalyst in the prior art has low activity when catalyzing olefin copolymerization, and the raw materials for preparing the catalyst are expensive and highly toxic. A metal complex and a preparation method and application thereof, as well as a preparation method for olefin copolymers are provided. When the metal complex is used to catalyze olefin copolymerization, the activity is high, and the raw materials for preparing the catalyst are cheap and low in toxicity, which is more conducive to industrial application.

[0011] In order to achieve the above object, the first aspect of the present invention provides a metal complex having a structure shown in formula (I):

[0012]

[0013] Wherein, R has the structure shown in formula (II),

[0014]

[0015] wherein M is selected from at least one of metals of Group IVB, Group VB, Group VIB, Group VIIB and Group VIII, X is oxygen or sulfur, and E1 is nitrogen or phosphorus;

[0016] R1 and R1' are each independently selected from hydrogen, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a heteroatom substituent; or, R1, R1' and the central carbon atom in formula (I) together form a 5-8 membered ring optionally containing a heteroatom substituent;

[0017] R3 and R4 are each independently selected from hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms and optionally containing a substituent, and a 5-8 membered ring containing or not containing a heteroatom and having a substituent or no substituent;

[0018] R7 is selected from one of hydrogen, halogen and a hydrocarbon group having 1-20 carbon atoms and optionally containing a heteroatom substituent; L1 is selected from one of a hydrocarbon group having 1-10 carbon atoms, a pyridine substituent, a piperidine substituent, an alkyl ether substituent, an aryl ether substituent, an alkyl aryl ether substituent, a cyclic ether substituent, an alkyl nitrile derivative substituent, an alcohol substituent, an amide substituent, an aliphatic ester substituent, an aromatic ester substituent, an amine substituent, a halogen and a cyclic unsaturated hydrocarbon substituent; or, L1 and R7 form a ring with each other, and the ring optionally has a substituent;

[0019] R2, R5, R6 are each independently selected from hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms and optionally containing a heteroatom or a heteroatom substituent, OR8, CO2R8, CO2A, C(O)N(R9)2, C(O)R8, SR8, SO2R8, SOR8, OSO2R8, P(O)(OR8) 2-y (R9) y , CN, NHR8, N(R8)2, Si(OR9) 3-x (R9) x 、OSi(OR9) 3-x (R9) x , NO2, SO3A, PO3A2, P(O)(OR8)2A and at least one of an epoxy-containing group, wherein the epoxy-containing group is a ring-containing C1-C6 alkyl group, and the number of ring carbon atoms in the oxygen-containing ring group is 2-10; R8 is selected from a hydrocarbon group having 1-20 carbon atoms, R9 is selected from hydrogen or a hydrocarbon group having 1-20 carbon atoms, A is selected from an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x is a natural number of 0-3, and y is a natural number of 0-2;

[0020] The heteroatoms are selected from oxygen, nitrogen, sulfur, phosphorus and silicon.

[0021] The second aspect of the present invention provides a method for preparing the metal complex as described above, the method comprising: reacting a compound represented by formula (III) with a complex C represented by the general formula ML′ to obtain a metal complex having a structure represented by formula (I);

[0022]

[0023] Wherein, R' has the structure shown in formula (IV),

[0024]

[0025] Wherein, the definitions of M and X, E1, R1, R1', R2, R3, R4, R5 and R6 in formula (III) and formula (IV) are the same as those in the first aspect;

[0026] Z is selected from hydrogen or a sulfinic acid group with a substituent, wherein the substituent is selected from hydrogen or C1-C 20 The hydrocarbon group;

[0027] L' is the general formula (R 10 )p(L2)q, wherein R 10is selected from hydrogen, halogen, a hydrocarbon group having 1-20 carbon atoms and optionally containing a heteroatom substituent, L2 is selected from a hydrocarbon group having 1-10 carbon atoms, a pyridine substituent, a piperidine substituent, an alkyl ether substituent, an aryl ether substituent, an alkyl aryl ether substituent, a cyclic ether substituent, an alkyl nitrile derivative substituent, an alcohol substituent, an amide substituent, an aliphatic ester substituent, an aromatic ester substituent, an amine substituent, a halogen and a cyclic unsaturated hydrocarbon substituent, and p and q are each independently an integer of 1-5;

[0028] Alternatively, L′ is two cyclooctadienyl ligands;

[0029] Alternatively, L' is three ligands, one of which is a cyclooctadienyl ligand, and the other two ligands are each independently selected from halogen and a hydrocarbon group having 1 to 10 carbon atoms.

[0030] The third aspect of the present invention provides use of the metal complex as described above in olefin copolymerization.

[0031] A fourth aspect of the present invention provides a method for preparing an olefin copolymer, the method comprising: subjecting a comonomer to a copolymerization reaction in the presence of a catalyst to obtain an olefin copolymer;

[0032] Wherein, the catalyst contains the metal complex described in the first aspect.

[0033] The metal complex provided by the present invention has significantly higher copolymerization activity when used to catalyze olefin copolymerization. In addition, the raw materials used to prepare the metal complex are cheap and low in toxicity, and are more suitable for application and have more industrial application prospects. DETAILED DESCRIPTION

[0034] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0035] In a first aspect, the present invention provides a metal complex having a structure shown in formula (I):

[0036]

[0037] Wherein, R has the structure shown in formula (II),

[0038]

[0039] wherein M is selected from at least one of metals of Group IVB, Group VB, Group VIB, Group VIIB and Group VIII, X is oxygen or sulfur, and E1 is nitrogen or phosphorus;

[0040] R1 and R1' are each independently selected from hydrogen, a hydrocarbon group having 1-20 (for example, 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 20) carbon atoms and optionally containing a heteroatom substituent; or, R1, R1' and the central carbon atom in formula (I) (in formula (I), the central carbon atom connecting the two R groups and R1 and R1') together form a 5-8 (for example, 5, 6, 7, 8) membered ring optionally containing a heteroatom substituent (that is, the ring may or may not have a heteroatom substituent, and the ring may be an aliphatic ring, an aromatic ring, or a ring containing a heteroatom selected from oxygen, nitrogen, and sulfur, etc.);

[0041] R3 and R4 are each independently selected from hydrogen, a chain hydrocarbon group having 1-20 (e.g., 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 20) carbon atoms and optionally containing a substituent (e.g., a heteroatom substituent), and a 5-8 membered ring containing or not containing a heteroatom and having a substituent or no substituent;

[0042] R7 is selected from one of hydrogen, halogen and a hydrocarbon group having 1-20 carbon atoms and optionally containing a heteroatom substituent, L1 is selected from one of a hydrocarbon group having 1-10 carbon atoms, a pyridine substituent, a piperidine substituent, an alkyl ether substituent, an aryl ether substituent, an alkyl aryl ether substituent, a cyclic ether substituent, an alkyl nitrile derivative substituent, an alcohol substituent, an amide substituent, an aliphatic ester substituent, an aromatic ester substituent, an amine substituent, a halogen and a cyclic unsaturated hydrocarbon substituent; or L1 and R7 form a ring with each other (may form a ring with 4-10 carbon atoms), and the ring optionally has a substituent;

[0043] R2, R5, and R6 are each independently selected from hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms and optionally containing a heteroatom or a heteroatom substituent (which may be a chain hydrocarbon group or a 5-8 membered ring with or without a substituent), OR8, CO2R8, CO2A, C(O)N(R9)2, C(O)R8, SR8, SO2R8, SOR8, OSO2R8, P(O)(OR8) 2-y (R9) y , CN, NHR8, N(R8)2, Si(OR9) 3-x (R9) x 、OSi(OR9) 3-x (R9) x, NO2, SO3A, PO3A2, P(O)(OR8)2A and at least one of an epoxy-containing group, wherein the epoxy-containing group is an oxygen-containing cyclic C1-C6 alkyl group (it can be understood that the oxygen-containing cyclic group has at least one oxygen atom) and the number of ring carbon atoms in the oxygen-containing cyclic group is 2-10; R8 is selected from a hydrocarbon group having 1-20 carbon atoms, R9 is selected from hydrogen or a hydrocarbon group having 1-20 carbon atoms, A is selected from an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x is a natural number of 0-3, and y is a natural number of 0-2;

[0044] The heteroatoms are selected from oxygen, nitrogen, sulfur, phosphorus and silicon.

[0045] The inventors of the present invention have found in their research that the above-mentioned metal complex has significantly higher catalytic activity when used as a catalyst for olefin copolymerization.

[0046] According to the present invention, preferably, R1 and R1' are independently selected from C1-C2 with or without heteroatom substituents. 10 Alkyl, C2-C 10 alkenyl, C2-C 10 Alkynyl and C6-C 20 aryl, more preferably each independently is methyl or trifluoromethyl; further preferably, R1 and R1' are the same;

[0047] Alternatively, R1, R1' and the central carbon atom in formula (I) together form a 6-membered ring (such as cyclohexyl).

[0048] According to the present invention, preferably, R2 is hydrogen or methyl, preferably hydrogen.

[0049] According to the present invention, preferably, R5 is hydrogen or methyl, preferably hydrogen.

[0050] According to the present invention, preferably, R6 is selected from hydrogen, methyl, anthracene, pyridyl, carbazolyl or a hydrocarbon group having 1-20 carbon atoms and having any number of fluorine substituents (for example, R6 can be pentafluorophenyl). When the R6 group is an electron-withdrawing group, the catalyst activity can be further improved, but the polymer molecular weight will be slightly reduced; when the R6 group is an electron-donating group, the polymer molecular weight will be further improved, but the catalyst activity will be slightly reduced. Those skilled in the art can select a suitable group according to actual needs.

[0051] According to the present invention, preferably, R3 is selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10Alkynyl, C6-C 20 One of the aryl groups, preferably phenyl or 2,6-dimethoxy-1-phenyl.

[0052] Preferably, R4 is selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C6-C 20 One of the aryl groups, preferably phenyl or 2,6-dimethoxy-1-phenyl.

[0053] The inventors of the present invention further discovered in their research that when R3 and R4 are selected from the above substituents, the metal complex can effectively inhibit the chain transfer phenomenon when used for olefin copolymerization while ensuring sufficient reaction of the monomers.

[0054] According to the present invention, preferably, M is selected from nickel or palladium, more preferably nickel. The inventors of the present invention further found in their research that when M is nickel, it can ensure that the metal complex has a high catalytic activity when applied to olefin polymerization, and can also significantly reduce the cost, which has obvious economic advantages.

[0055] According to the present invention, preferably, X is oxygen.

[0056] According to the present invention, preferably, E1 is phosphorus.

[0057] According to the present invention, preferably, R7 and L1 are mutually cyclically cyclooctenyl; or, R7 is halogen, more preferably chlorine; L1 is C1-C 10 The hydrocarbon group is preferably a methyl group.

[0058] According to the present invention, preferably, the metal complex is selected from the group consisting of the following metal complexes:

[0059] Metal complex 1: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are phenyl groups, R2, R5 and R6 are hydrogen groups, and R7 and L1 are cyclically connected to form a cyclooctenyl group;

[0060] Metal complex 2: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2, R5 and R6 are hydrogen, and R7 and L1 form a ring with each other to form a cyclooctenyl group;

[0061] Metal complex 3: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2 and R5 are hydrogen, R6 is methyl group, and R7 and L1 are cyclically connected to form a cyclooctenyl group;

[0062] Metal complex 4: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2 and R5 are hydrogen, R6 is anthracene, and R7 and L1 form a ring with each other to form a cyclooctenyl group;

[0063] Metal complex 5: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are trifluoromethyl, R3 and R4 are phenyl, R2 and R5 are hydrogen, R6 is pyridyl, and R7 and L1 form a ring with each other to form a cyclooctenyl;

[0064] Metal complex 6: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2 and R5 are hydrogen groups, R6 is pentafluorophenyl group, and R7 and L1 are mutually cyclically formed into a cyclooctenyl group;

[0065] Metal complex 7: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are phenyl groups, R2, R5 and R6 are hydrogen groups, R7 is chlorine, and L1 is methyl group;

[0066] Metal complex 8: M is palladium, X is oxygen, E1 is phosphorus, R1 and R1' together with the central carbon atom in formula (I) form a cyclohexyl group, R3 and R4 are phenyl groups, R2 and R5 are hydrogen, R6 is a carbazolyl group, R7 is chlorine, and L1 is a methyl group;

[0067] Metal complex 9: M is nickel, X is oxygen, E1 is phosphorus, R1 is methyl, R3 and R4 are 2,6-dimethoxy-1-phenyl, R2 and R5 are methyl, R6 is methyl, and R7 and L1 form a cyclooctenyl ring.

[0068] In a second aspect, the present invention provides a method for preparing the metal complex as described above, the method comprising: reacting a compound represented by formula (III) with a complex C represented by the general formula ML′ to obtain a metal complex having a structure represented by formula (I);

[0069]

[0070] Wherein, R' has the structure shown in formula (IV),

[0071]

[0072] Wherein, the definitions of M and X, E1, R1, R1', R2, R3, R4, R5 and R6 in formula (III) and formula (IV) are the same as those in the first aspect;

[0073] Z is selected from hydrogen or a sulfinic acid group with a substituent, wherein the substituent is selected from hydrogen or C1-C 20 The hydrocarbon group;

[0074] L' is the general formula (R 10 )p(L2)q, wherein R 10 is selected from hydrogen, halogen, a hydrocarbon group having 1-20 carbon atoms and optionally containing a heteroatom substituent, L2 is selected from a hydrocarbon group having 1-10 carbon atoms, a pyridine substituent, a piperidine substituent, an alkyl ether substituent, an aryl ether substituent, an alkyl aryl ether substituent, a cyclic ether substituent, an alkyl nitrile derivative substituent, an alcohol substituent, an amide substituent, an aliphatic ester substituent, an aromatic ester substituent, an amine substituent, a halogen and a cyclic unsaturated hydrocarbon substituent, and p and q are each independently an integer of 1-5;

[0075] Alternatively, L′ is two cyclooctadienyl ligands;

[0076] Alternatively, L' is three ligands, one of which is a cyclooctadienyl ligand, and the other two ligands are each independently selected from halogen and a hydrocarbon group having 1 to 10 carbon atoms (such as methyl).

[0077] Wherein, after the compound represented by formula (III) reacts with complex C, the Z part can leave. The number of p and q is also based on maintaining the charge of complex C to zero.

[0078] According to the present invention, preferably, the molar ratio of the compound represented by formula (III) to the complex C is 1:(0.01-99), more preferably 1:(2-10).

[0079] According to the present invention, preferably, the reaction conditions include: temperature of 0-100° C., and time of 1 s-24 h.

[0080] Further preferably, the reaction conditions include: a temperature of 20-60°C (for example, 20°C, 30°C, 40°C, 50°C, 60°C, and a range formed by any two of the above values ​​and a value within the range), and a time of 1-3h (for example, 1h, 2h, 3h). The reaction can be carried out under stirring, and the stirring rate can be 100-300rpm.

[0081] According to the present invention, preferably, the reaction is carried out in the presence of a solvent and an inert gas, and the solvent is selected from toluene and / or (normal) hexane. The inert atmosphere refers to a gas that does not participate in the above reaction, for example, it can be a nitrogen, helium or argon atmosphere. The amount of the solvent is not particularly limited, as long as it can fully disperse the reaction materials.

[0082] The complex C can be first dissolved in a solvent (such as toluene, the mass ratio of complex C to solvent is 1 mg: (0.1-5) mL), and then the obtained solution and the compound shown in formula (III) (the compound shown in formula (III) can be used in the form of a solid) are mixed. After the reaction is completed, the prepared metal complex can be separated from other components in the material obtained after the reaction (the separation method is not limited, as long as it does not affect the chemical structure of the metal complex, such as recrystallization) and then stored, or the above separation can be omitted and the material obtained by the reaction can be directly stored. It can be stored in a high-purity nitrogen environment. When used for catalytic olefin copolymerization, the prepared pure metal complex can be used, or the material obtained after the above reaction can be directly used without purification.

[0083] According to the present invention, preferably, the complex C is selected from bis-1,5-cyclooctadiene nickel, chloro-1,5-cyclooctadiene-methyl-nickel or chloro-1,5-cyclooctadiene-methyl-palladium.

[0084] The method for obtaining the compound represented by formula (III) is not particularly limited and can be synthesized by itself. When each group therein is determined and the structure of the compound represented by formula (III) is completely determined, a person skilled in the art can synthesize the compound. For example, when X is oxygen, E1 is phosphorus, R1 and R1' are methyl, R3 and R4 are phenyl, R2, R5 and R6 are hydrogen, and Z is hydrogen, the preparation method of the compound represented by formula (III) can be:

[0085] Under the condition of -40°C to -60°C, isopropyl magnesium chloride is slowly added (can be added dropwise, isopropyl magnesium chloride can be used in the form of a tetrahydrofuran solution) to a tetrahydrofuran (THF) solution of iodobenzene, then slowly warmed to room temperature and reacted for 0.5-2h, then the reaction solution is cooled to -60°C to -85°C, and phosphorus trichloride is slowly added (can be added dropwise), then slowly warmed to room temperature and reacted for 0.5-2h, and the first intermediate is obtained after the solvent is removed under reduced pressure. Wherein, relative to 1g of iodobenzene, the amount of isopropyl magnesium chloride can be 0.1-0.8g, and the amount of phosphorus trichloride can be 0.05-0.5g.

[0086] Dissolve bisphenol A in THF, add a strong base (such as NaH, the mass ratio of bisphenol A and NaH can be 10: (2.5-4)) at -5°C to 0°C and stirring, and react for 1.5-3 hours after naturally returning to room temperature. Then cool to -5°C to 0°C, slowly add chloromethyl methyl ether (the mass ratio of bisphenol A and chloromethyl methyl ether can be 10: (7-8)), and react for 2-4 hours after naturally returning to room temperature. After the reaction is completed, wash with water and extract with ethyl acetate. The organic phase after extraction is washed with 0.5-1mol / L KOH or NaOH solution (can be washed 1-3 times), and then washed with deionized water (can be washed 1-3 times), separate the organic phase, dry it with anhydrous sodium sulfate, and filter it after drying. The filtrate is concentrated by rotary evaporation and simply purified with a silica gel column. The product is the second intermediate (also known as the bisphenol A hydroxyl protection intermediate).

[0087] Then the second intermediate is dissolved in THF, and n-butyl lithium is slowly added thereto at 0-3°C in an argon atmosphere (n-butyl lithium can be used in the form of a toluene solution, and the mass ratio of the second intermediate to n-butyl lithium can be 1: (0.001-0.4) g). After naturally returning to room temperature, the reaction is carried out for 2-4 hours, and then the temperature is lowered to 0-3°C. The first intermediate is dissolved in THF and slowly added to the above-reacted material (the mass ratio of the first intermediate to the second intermediate can be 1: (0.8-1.4)), and then naturally returned to room temperature and reacted for 10-15 hours. Subsequently, a degassed saturated aqueous solution of ammonium chloride is added, and after separating the organic phase, the aqueous phase is extracted with ether, and the organic phase is washed with brine. Subsequently, it is dried with anhydrous sodium sulfate to obtain an ether solution. The ether solution can be bubbled with HCl gas for 20-30 minutes at -70 to 80°C, and then stirred for 10-15 hours after naturally returning to room temperature, and then the solvent is removed by distillation.

[0088] After distillation, the distilled material is redissolved in ether (the ratio of the distilled material to ether can be 1g: (40mL-60mL)), NH3 gas is bubbled at -70°C to 80°C for 25-35 minutes, and stirred for 10-15 hours after naturally returning to room temperature. Then, after distilling the solvent, wash with an appropriate amount of n-hexane, remove solid impurities, and evaporate the solvent to obtain the compound represented by formula (III).

[0089] In a third aspect, the present invention provides use of the metal complex as described above in olefin copolymerization.

[0090] In a fourth aspect, the present invention provides a method for preparing an olefin copolymer, the method comprising: subjecting a comonomer to a copolymerization reaction in the presence of a catalyst to obtain an olefin copolymer;

[0091] Wherein, the catalyst contains the metal complex as described above.

[0092] According to the present invention, preferably, the comonomer comprises α-olefin and acrylate.

[0093] α-olefins generally have a structure such as CH2=CHR 11 The structure of R 11 It may be hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a branch, a ring and / or an unsaturated bond.

[0094] Acrylates generally have a structure such as CH2=CHR 12 CO2R 13 The structure of R 12 It can be hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group can have a branch, a ring and / or an unsaturated bond. 13 It can be hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group may have a branch, a ring and / or an unsaturated bond. 13 A heteroatom may be contained at any position therein.

[0095] According to a preferred embodiment of the present invention, the α-olefin is ethylene, and the acrylic ester is methyl methacrylate.

[0096] According to the present invention, preferably, the amount of the catalyst used is 0.1-0.6 mol, more preferably 0.2-0.4 mol (for example, 0.2 mol, 0.3 mol, 0.4 mol) relative to 100 mol of acrylate. The use form of the catalyst is not particularly limited, for example, the catalyst can be used directly, or the catalyst can be supported on a carrier and then used. The carrier is not particularly limited, for example, it can be silica gel, clay or other composite materials.

[0097] Preferably, the conditions of the copolymerization reaction include: a temperature of -20 to 290°C, preferably 20 to 60°C (for example, it can be 20°C, 30°C, 40°C, 50°C, 60°C and the range formed by any two of the above values ​​and the value within the range), a polymerization pressure of 0.1MPa-100MPa, preferably 0.1-1MPa, and a polymerization time of 1s-10h, preferably 1-3h (for example, it can be 1h, 2h, 3h). It can be understood that in the copolymerization reaction, generally, acrylate and catalyst are added to the reaction vessel, and then ethylene is introduced into the system to maintain the reaction at a predetermined pressure. The amount of ethylene is based on maintaining the predetermined pressure. Generally, in order to maintain the pressure, the amount of ethylene introduced will be greater than the amount of ethylene that can participate in the copolymerization reaction.

[0098] The copolymerization reaction is carried out in an organic solvent that has been fully dehydrated and deoxygenated by any chemical or physical method, and the organic solvent is preferably toluene or hexane.

[0099] Wherein, the polymerization process and polymerization device of copolymerization reaction are not particularly limited. The polymerization process can be selected from slurry polymerization with solvent (the solvent can be toluene), slurry bulk polymerization without solvent and using liquefied monomer itself as medium, gas phase polymerization and other forms. The copolymerization reaction device can be selected from batch reactor type, semi-batch type, and continuous type. After reaching the copolymerization time, nitrogen can be introduced into the reactor to blow out the ethylene and polar monomers that do not participate in the reaction to terminate the copolymerization reaction.

[0100] In the copolymerization reaction, one or more of the above metal complexes can be used. The inventors of the present invention have also found that when more than one of the above metal complexes are used together, the molecular weight distribution can be broadened and the polar monomer insertion rate can be increased.

[0101] The present invention will be described in detail below through examples.

[0102] In the following examples, Ni(COD)2 represents bis-1,5-cyclooctadiene nickel (0), where 0 represents the valence state of nickel.

[0103] Example 1

[0104] 8 g of iodobenzene was dissolved in 100 mL of dry THF, and a THF solution of isopropyl magnesium chloride (the concentration of isopropyl magnesium chloride was 2 mol / L and the amount of solution was 16.5 mL) was slowly added thereto at -50°C. The above materials were slowly heated to room temperature under stirring and reacted for 1 hour. Then cooled to -78°C, 2 g of phosphorus trichloride was slowly added thereto, the materials were slowly heated to room temperature under stirring and reacted for 1 hour, and the solvent was removed under reduced pressure to obtain intermediate 1. The reaction equation of the reaction is shown below.

[0105]

[0106] Example 2

[0107] 8g of 2,6-dimethoxyiodobenzene was dissolved in 100mL of dry THF, and a THF solution of isopropyl magnesium chloride (the concentration of isopropyl magnesium chloride was 2 mol / L and the amount of solution was 16.5mL) was slowly added thereto at -50°C. The above materials were slowly heated to room temperature under stirring and reacted for 1 hour. Then the mixture was cooled to -78°C, 2g of phosphorus trichloride was slowly added thereto, the materials were slowly heated to room temperature under stirring and reacted for 1 hour, and the solvent was removed under reduced pressure to obtain intermediate 2. The reaction equation of the reaction is shown below.

[0108]

[0109] Example 3

[0110] Dissolve 10g of bisphenol A in THF (100mL), slowly add a THF solution of sodium hydride (2.91g NaH, 200mL THF) at 0℃ and under continuous stirring. React for 2 hours after naturally returning to room temperature. Then cool to 0℃, slowly add 7.76g of chloromethyl methyl ether, and react for 3 hours after naturally returning to room temperature. After the reaction is completed, wash with water and extract with ethyl acetate. After extraction, the organic phase is washed once with 1mol / L KOH solution, and then washed twice with deionized water. After re-separating the organic phase, dry it with anhydrous sodium sulfate, and filter it after drying. The filtrate is concentrated by rotary evaporation and simply purified with a silica gel column. The product is the second intermediate.

[0111] The second intermediate 0.75g was dissolved in 30mL THF, and 1.2mL of n-butyl lithium concentration was slowly added to 2.5mol / L n-butyl lithium toluene solution at 0°C in an argon atmosphere. The reaction was carried out for 3 hours after naturally returning to room temperature. The temperature was then lowered to 0°C, and 700mg of the intermediate 1 prepared in Example 1 was dissolved in 15mL THF, and the resulting solution was slowly dripped into the material after the above reaction, and the reaction was carried out for 12 hours after naturally returning to room temperature. Subsequently, 10mL of degassed saturated ammonium chloride aqueous solution was added, and after separating the organic phase, the aqueous phase was extracted with ether, and the organic phase was washed with brine. It was then dried over anhydrous sodium sulfate.

[0112] HCl gas was bubbled into the ether solution obtained above at -78°C for 25 minutes. After the solution was naturally returned to room temperature and stirred for 12 hours, the solvent was distilled off.

[0113] After distillation, the product was redissolved in ether (dissolution ratio of 1 g: 50 mL), NH3 gas was bubbled at -78 ° C for 30 minutes, and the mixture was naturally restored to room temperature and stirred for 12 hours. After distilling the solvent, it was washed with n-hexane, and the solid impurities were removed and the solvent was evaporated to obtain a compound represented by formula (III), and the structure was shown in formula (a).

[0114]

[0115] Take 10 mg of the compound represented by the above formula (III) and put it into a 5 mL reaction bottle. Weigh 14 mg of Ni(COD)2 and mix it with 10 mL of toluene to obtain a toluene solution of Ni(COD)2. Take 2 mL of the toluene solution of Ni(COD)2 and add it to the above reaction bottle (then the molar ratio of the compound represented by formula (III) to Ni(COD)2 is 1:2), and stir it in a closed nitrogen atmosphere at 25°C for 1 hour (stirring rate is 200 rpm) and then let it stand for use.

[0116] Example 4

[0117] The reaction was carried out in the manner of Example 3, except that the intermediate 1 prepared in Example 1 was replaced by the intermediate 2 prepared in Example 2; the molar ratio of the obtained compound of formula (III) (the structural formula is shown in formula (b) below) and Ni(COD)2 was 1:3, the reaction temperature was 20°C, and the mixture was stirred in a closed nitrogen atmosphere for 2 h (stirring rate was 200 rpm) and then allowed to stand for use.

[0118]

[0119] Example 5

[0120] The method of Example 4 was followed, except that bisphenol A was replaced with methyl-modified bisphenol A as shown in the following formula (c). The molar ratio of the obtained compound of formula (III) (shown in the following formula (d)) to was 1:4, the reaction temperature was 30° C., and the mixture was stirred in a closed nitrogen atmosphere for 3 h (stirring rate was 200 rpm) and then allowed to stand for use.

[0121]

[0122] Example 6

[0123] The method of Example 4 is followed, except that the bisphenol A is replaced by a molecule of the following formula (e). The structure of the compound of the obtained formula (III) is shown in formula (f).

[0124]

[0125]

[0126] Example 7

[0127] The method of Example 3 is followed, except that the bisphenol A is replaced by a molecule of the following formula (g). The structure of the compound of the obtained formula (III) is shown in formula (h).

[0128]

[0129] Example 8

[0130] The method of Example 4 is followed, except that the bisphenol A is replaced by a molecule of the following formula (i). The structure of the compound of the obtained formula (III) is shown in formula (j).

[0131]

[0132]

[0133] Example 9

[0134] The process was carried out in the manner of Example 3, except that Ni(COD)2 was replaced by (COD)1Ni(Me)1Cl.

[0135] Example 10

[0136] The method of Example 3 is followed, except that bisphenol A is replaced by a molecule having a structure shown in the following formula (k). The structure of the compound of the obtained formula (III) is shown in the formula (l). Ni(COD)2 is replaced by (COD)1Pd(Me)1Cl.

[0137]

[0138] Embodiment 11

[0139] The method of Example 5 is followed, except that bisphenol A is replaced by a molecule having a structure shown in the following formula (m). The structure of the compound of the obtained formula (III) is shown in formula (n).

[0140]

[0141] Comparative Example 1

[0142] The catalyst in Example 9 of CN106632507B.

[0143] Comparative Example 2

[0144] The catalyst described in Example 25 of CN109320558A.

[0145] The metal complexes prepared in the above embodiments were characterized by hydrogen, carbon and phosphorus spectra, and their structures were determined as shown in Table 1. In Table 1, taking the structure corresponding to Embodiment 3 as an example, the phenyl group connected to P and the bracket with the subscript 2 indicate that P is connected to two phenyl groups respectively.

[0146] Table 1

[0147]

[0148]

[0149]

[0150] Test Case

[0151] The metal complex prepared in Example 3-11 is copolymerized in the following manner: toluene (40 mL) after anhydrous treatment and a predetermined amount of methyl methacrylate (MMA) are loaded into an autoclave with a volume of about 100 mL and equipped with a stirring paddle. After the autoclave is heated to a predetermined temperature under stirring, ethylene is introduced, and the temperature and pressure are adjusted to predetermined conditions. After the adjustment is completed, a catalyst is added for copolymerization. During the reaction, the amount of ethylene introduced is controlled to maintain the pressure in the autoclave at the corresponding value in the table. After reaching the predetermined polymerization time, nitrogen is introduced into the reactor to discharge the unreacted gas. Take out the solid reaction product and dry it to a constant weight.

[0152] For the product of Comparative Example 1, the copolymerization reaction conditions of Example 9 in Table 1 of CN106632507B were followed.

[0153] For the product of Comparative Example 2, the copolymerization steps in Example 25 of CN109320558A were followed.

[0154] The catalyst used, copolymerization pressure, MMA dosage, copolymerization temperature and copolymerization time are shown in Table 2.

[0155] Table 2

[0156]

[0157] For the products prepared by the above reactions, the following measurements were performed:

[0158] (1) Tm (melting point) and Tc (crystallization temperature): Determined by DSC (differential scanning calorimeter) measurement:

[0159] Using PYRIS Diamond DSC (PerkinElmer Inc.), a sample (about 5 mg) was melted at 210° C. for 5 minutes, then the temperature was reduced to -20° C. at a rate of 10° C. / min, and after the temperature was maintained at -20° C. for 5 minutes, the temperature was increased to 210° C. at a rate of 10° C. / min to obtain a melting curve. The highest temperature of the main exothermic peak in the temperature reduction step was defined as the crystallization temperature Tc. In addition, the peak top temperature of the main endothermic peak in the last temperature increase step performed to obtain the melting curve was defined as the melting point Tm.

[0160] (2) Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn, determined by GPC measurement:

[0161] First, a sample (about 20 mg) was collected in a vial for a pretreatment unit PL-SP 260VS for high temperature GPC manufactured by Polymer Laboratories Ltd, and o-dichlorobenzene (wherein BHT concentration = 0.5 g / L) containing BHT (2,6-di-tert-butyl-4-methylphenol) as a stabilizer was added thereto, and the polymer concentration was adjusted to 0.1 wt%. The polymer was dissolved in the above-mentioned pretreatment unit PL-SP 260VS for high temperature GPC by heating at 135°C, and filtered with a glass filter to prepare a sample solution. No polymer was captured by the glass filter in the GPC measurement. Next, the GPC measurement was performed using a TSKgelGMH-HT (30 cm×4) column manufactured by TosohCorp. and a GPCV2000RI detector manufactured by Waters. The following measurement conditions were adopted: sample solution injection amount: about 520 (μL); column temperature: 135°C; solvent: o-dichlorobenzene; flow rate = 1.0 (mL / min). The molecular weight was calculated as follows: a commercially available monodisperse polystyrene was used as a standard sample, a calibration curve of retention time and molecular weight was obtained from the polystyrene standard sample and the viscosity formula of polyolefin, and the molecular weight was calculated based on the calibration curve. As the viscosity formula, [η] = K × Mα was used, and for polystyrene, K = 1.38E-4, α = 0.70 was used; and for ethylene polymers, K = 4.77E-4, α = 0.70 was used.

[0162] In each copolymerization reaction, the catalyst activity Vp represents the ratio of the copolymer yield (kg) obtained per hour to the metal in the catalyst used for the copolymerization per 1 mol. The larger the Vp, the higher the catalyst activity.

[0163] The results are shown in Table 3.

[0164]

[0165] It can be seen from the results in Table 1 that the metal complex of the present invention has higher activity when catalyzing olefin copolymerization. In addition, the raw materials for preparing the metal complex provided by the present invention, nickel and bisphenol A, are cheap and low in toxicity, which is more conducive to industrial application.

[0166] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A metal complex, characterized in that The metal complex has a structure shown in formula (I): Wherein, R has the structure shown in formula (II), wherein M is selected from at least one of metals of Group IVB, Group VB, Group VIB, Group VIIB and Group VIII, X is oxygen or sulfur, and E1 is nitrogen or phosphorus; R1 and R1' are each independently selected from hydrogen, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a heteroatom substituent; or, R1, R1' and the central carbon atom in formula (I) together form a 5-8 membered ring optionally containing a heteroatom substituent; R3 and R4 are each independently selected from hydrogen, a chain hydrocarbon group having 1 to 20 carbon atoms and optionally containing a substituent, and a 5-8 membered ring containing or not containing a heteroatom and having a substituent or no substituent; R7 is selected from one of hydrogen, halogen and a hydrocarbon group having 1-20 carbon atoms and optionally containing a heteroatom substituent; L1 is selected from one of a hydrocarbon group having 1-10 carbon atoms, a pyridine substituent, a piperidine substituent, an alkyl ether substituent, an aryl ether substituent, an alkyl aryl ether substituent, a cyclic ether substituent, an alkyl nitrile derivative substituent, an alcohol substituent, an amide substituent, an aliphatic ester substituent, an aromatic ester substituent, an amine substituent, a halogen and a cyclic unsaturated hydrocarbon substituent; or, L1 and R7 form a ring with each other, and the ring optionally has a substituent; R2, R5, R6 are each independently selected from hydrogen, halogen, a hydrocarbon group having 1 to 30 carbon atoms and optionally containing a heteroatom or a heteroatom substituent, OR8, CO2R8, CO2A, C(O)N(R9)2, C(O)R8, SR8, SO2R8, SOR8, OSO2R8, P(O)(OR8) 2-y (R9) y , CN, NHR8, N(R8)2, Si(OR9) 3-x (R9) x 、OSi(OR9) 3-x (R9) x , NO2, SO3A, PO3A2, P(O)(OR8)2A and at least one of an epoxy-containing group, wherein the epoxy-containing group is an oxygen-containing ring group C1-C6 alkyl and the number of ring carbon atoms of the oxygen-containing ring group is 2-10; R8 is selected from a hydrocarbon group having 1-20 carbon atoms, R9 is selected from hydrogen or a hydrocarbon group having 1-20 carbon atoms, A is selected from an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x is a natural number of 0-3, and y is a natural number of 0-2; The heteroatoms are selected from oxygen, nitrogen, sulfur, phosphorus and silicon.

2. The metal complex according to claim 1, wherein R1 and R1' are each independently selected from C1-C 10 Alkyl, C2-C 10 alkenyl, C2-C 10 Alkynyl and C6-C 20 The aryl groups are preferably independently methyl or trifluoromethyl; more preferably, R1 and R1' are the same, Alternatively, R1, R1' and the central carbon atom in formula (I) together form a 6-membered ring.

3. The metal complex according to claim 1 or 2, wherein R2 is hydrogen or methyl, preferably hydrogen; and / or, R5 is hydrogen or methyl, preferably hydrogen; and / or, R6 is selected from hydrogen, methyl, anthracenyl, pyridyl, carbazolyl or a hydrocarbon group having 1 to 20 carbon atoms and having any number of fluorine substituents; And / or, R3 is selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C6-C 20 One of the aryl groups of , preferably phenyl or 2,6-dimethoxy-1-phenyl; and / or, R4 is selected from C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 Alkynyl, C6-C 20 One of the aryl groups of , preferably phenyl or 2,6-dimethoxy-1-phenyl; and / or, M is selected from nickel or palladium, preferably nickel; and / or, X is oxygen; and / or, E1 is phosphorus; Preferably, R7 and L1 are mutually cyclically cyclooctenyl; or, R7 is halogen, preferably chlorine; L1 is C1-C 10 The hydrocarbon group is preferably a methyl group.

4. The metal complex according to claim 1 or 2, wherein The metal complex is selected from the group consisting of the following metal complexes: Metal complex 1: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are phenyl groups, R2, R5 and R6 are hydrogen groups, and R7 and L1 are cyclically connected to form a cyclooctenyl group; Metal complex 2: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2, R5 and R6 are hydrogen, and R7 and L1 form a ring with each other to form a cyclooctenyl group; Metal complex 3: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2 and R5 are hydrogen, R6 is methyl group, and R7 and L1 are cyclically connected to form a cyclooctenyl group; Metal complex 4: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2 and R5 are hydrogen, R6 is anthracene, and R7 and L1 form a ring with each other to form a cyclooctenyl group; Metal complex 5: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are trifluoromethyl, R3 and R4 are phenyl, R2 and R5 are hydrogen, R6 is pyridyl, and R7 and L1 form a ring with each other to form a cyclooctenyl; Metal complex 6: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are 2,6-dimethoxy-1-phenyl groups, R2 and R5 are hydrogen groups, R6 is pentafluorophenyl group, and R7 and L1 are mutually cyclically formed into a cyclooctenyl group; Metal complex 7: M is nickel, X is oxygen, E1 is phosphorus, R1 and R1' are methyl groups, R3 and R4 are phenyl groups, R2, R5 and R6 are hydrogen groups, R7 is chlorine, and L1 is methyl group; Metal complex 8: M is palladium, X is oxygen, E1 is phosphorus, R1, R1' and the central carbon atom in formula (I) together form a cyclohexyl group, R3 and R4 are phenyl groups, R2 and R5 are hydrogen, R6 is a carbazolyl group, R7 is chlorine, and L1 is a methyl group; Metal complex 9: M is nickel, X is oxygen, E1 is phosphorus, R1 is methyl, R3 and R4 are 2,6-dimethoxy-1-phenyl, R2 and R5 are methyl, R6 is methyl, and R7 and L1 form a cyclooctenyl ring.

5. A method for preparing the metal complex according to any one of claims 1 to 4, characterized in that: The method comprises: reacting a compound represented by formula (III) with a complex C represented by the general formula ML′ to obtain a metal complex having a structure represented by formula (I); Wherein, R' has the structure shown in formula (IV), Wherein, the definitions of M and X, E1, R1, R1', R2, R3, R4, R5 and R6 in formula (III) and formula (IV) are the same as those in claims 1 to 4; Z is selected from hydrogen or a sulfinic acid group with a substituent, wherein the substituent is selected from hydrogen or C1-C 20 The hydrocarbon group; L' is the general formula (R 10 )p(L2)q, wherein R 10 is selected from hydrogen, halogen, a hydrocarbon group having 1-20 carbon atoms and optionally containing a heteroatom substituent, L2 is selected from a hydrocarbon group having 1-10 carbon atoms, a pyridine substituent, a piperidine substituent, an alkyl ether substituent, an aryl ether substituent, an alkyl aryl ether substituent, a cyclic ether substituent, an alkyl nitrile derivative substituent, an alcohol substituent, an amide substituent, an aliphatic ester substituent, an aromatic ester substituent, an amine substituent, a halogen and a cyclic unsaturated hydrocarbon substituent, and p and q are each independently an integer of 1-5; Alternatively, L′ is two cyclooctadienyl ligands; Alternatively, L' is three ligands, one of which is a cyclooctadienyl ligand, and the other two ligands are each independently selected from halogen and a hydrocarbon group having 1 to 10 carbon atoms.

6. The method according to claim 5, wherein: The molar ratio of the compound represented by formula (III) to the complex C is 1:(0.01-99), preferably 1:(2-10); And / or, the reaction conditions include: temperature of 0-100°C, preferably 20-60°C, time of 1s-24h, preferably 1-3h; And / or, the reaction is carried out in the presence of a solvent and in an inert gas atmosphere, and the solvent is selected from toluene and / or hexane.

7. The method according to claim 6, wherein: The complex C is selected from bis-1,5-cyclooctadiene nickel, chloro-1,5-cyclooctadiene-methyl-nickel or chloro-1,5-cyclooctadiene-methyl-palladium.

8. Use of the metal complex according to any one of claims 1 to 4 in olefin copolymerization.

9. A method for preparing an olefin copolymer, characterized in that: The method comprises: in the presence of a catalyst, copolymerizing a comonomer to obtain an olefin copolymer; Wherein, the catalyst contains the metal complex described in any one of claims 1-4.

10. The method according to claim 9, wherein: The comonomer comprises an α-olefin and an acrylate; Preferably, the α-olefin is ethylene, and the acrylate is methyl methacrylate; Preferably, the amount of the catalyst is 0.1-0.6 mol, more preferably 0.2-0.4 mol, relative to 100 mol of acrylate; And / or, the conditions of the copolymerization reaction include: temperature of -20°C to 290°C, preferably 20 to 60°C, polymerization pressure of 0.1MPa-100MPa, preferably 0.1-1MPa, polymerization time of 1s-10h, preferably 1-3h.

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