Process for preparing olefin-polar monomer copolymers

Abstract

To provide a method for preparing an olefin-olefinic alcohol copolymer, by which a spherical and / or spherical-like polymer having a good form can directly be obtained without requiring a subsequent treatment such as granulation, and to provide the olefin-olefinic alcohol copolymer produced by the method.SOLUTION: The catalyst used in the process for preparing the olefin-olefinic alcohol copolymer comprises a diimine metal complex as shown in Formula I. The spherical and / or spherical-like morphology of the polymer produced according to the preferred embodiment of the preparation method has good expectations in industrial applications.SELECTED DRAWING: Figure 1

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention is in the field of high molecular weight polymer preparation, and specifically relates to a method for preparing olefin-polar monomer copolymers.

[0002] [Background technology] Polyolefin products are inexpensive, have excellent performance, and have a wide range of applications. By introducing polar groups into polyolefin molecular chains through chemical synthesis under conditions that preserve the inherently excellent physical and chemical properties of polyolefins, their chemical inertness, printability, wettability, and compatibility with other materials can be improved, thereby endowing polyolefins with new properties not possessed by their raw materials. Currently, in the industrial field, high-pressure free-radical polymerization is primarily used to promote the direct copolymerization of olefins with polar monomers. For example, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-acrylic acid copolymer are produced by this method. While high-pressure free-radical copolymerization can directly introduce copolymerizable polar monomers into polyolefin chains, this method requires high temperature and pressure conditions, high energy consumption, and expensive equipment.

[0003] Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is a novel polymeric material that combines the processability of ethylene polymers with the gas barrier properties of vinyl alcohol polymers. It is one of the three major barrier resins currently produced industrially worldwide and is widely used in food packaging, pharmaceuticals, and other products. Vinyl alcohol cannot exist independently as a monomer. Therefore, ethylene-vinyl alcohol copolymers are typically produced by preparing ethylene-vinyl acetate copolymers by free radical polymerization and then alcoholizing the ethylene-vinyl acetate copolymer. However, the alcoholysis process requires a large amount of solvent, and the final saponified product contains many impurities, such as acetic acid and alkali metal salts, which must be washed away with large amounts of water.

[0004] Coordination-catalyzed copolymerization as a polymer preparation technique at ambient temperature and pressure has attracted widespread attention due to its important role in reducing energy consumption and improving reaction efficiency. The involvement of catalysts in the reaction process significantly reduces the activation energy of copolymerization of olefinic and polar monomers, which is beneficial for obtaining functional polymers with higher molecular weights at lower temperatures and pressures. Currently, only a few literature studies have reported on the use of transition metal complexes to catalyze the copolymerization of olefins with unsaturated alcohols or unsaturated carboxylic acids. However, in the prior art, regardless of the method used for polymerization, the resulting polymers are viscous block solids, which are prone to clogging in the polymerization equipment and make polymer transportation, solvent removal, granulation, etc. difficult.

[0005] [DISCLOSURE OF THE INVENTION] The object of the present invention is to overcome the drawbacks of the prior art and provide a method for preparing an olefin-polar monomer copolymer. The method provided by the present invention can directly obtain spherical and / or spherical-like polymers with good morphology without requiring subsequent processing such as granulation. Therefore, the method of the present invention is expected to be well applied industrially.

[0006] In a first aspect, the present invention provides a method for preparing an olefin-polar monomer copolymer, comprising copolymerizing an olefin and a polar monomer in the presence of a catalyst and optionally a chain transfer agent to prepare the olefin-polar monomer copolymer, the catalyst comprising a main catalyst and optionally a co-catalyst, the main catalyst being a diimine-metal complex represented by formula 1:

[0007] [ka]

[0008] wherein R1 and R2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; R3 and R4 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, and C1-C20 hydrocarbyl with or without a substituent Q, and adjacent R3 and R4 groups are optionally joined to form a ring or ring system; and each R 11 are independently C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA non-metallic atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q; Or an amino-imine metal complex represented by formula 1':

[0009] [ka]

[0010] wherein R1 and R2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; each R3 is independently selected from the group consisting of hydrogen and a C1-C20 hydrocarbyl with or without a substituent Q; each R5 through R8 are independently selected from the group consisting of hydrogen, halogen, hydroxy, and a C1-C20 hydrocarbyl with or without a substituent Q, and the R5 through R8 groups are optionally joined to form a ring or ring system; each R 12 are independently C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA non-metallic atom; each M is independently a Group VIII metal; and each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q.

[0011] The term "polar monomer," as used herein, refers to a monomer having at least one polar group, such as a hydroxyl group, a carboxyl group, an acid anhydride group, and at least one coordinatively polymerizable unsaturated bond. The polar monomer has 2 to 20 carbon atoms (e.g., 2 to 16 carbon atoms, e.g., 2 to 12 carbon atoms, e.g., 2 to 10 carbon atoms). In some embodiments, the polar monomer is selected from the group consisting of olefinic monomers having one or more hydroxyl groups and / or one or more carboxyl groups, preferably α-olefinic monomers (also called vinyl monomers) having one or more hydroxyl groups and / or one or more carboxyl groups.

[0012] In a subembodiment of the process of the present invention, the polar monomer is selected from the group consisting of olefinic monomers having one or more hydroxy groups, or the polar monomer is selected from the group consisting of olefinic monomers having one or more carboxyl groups, and the main catalyst comprises a diimine metal complex represented by formula Ib.

[0013] [ka]

[0014] wherein R1 and R2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; R5-R8 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, and C1-C20 hydrocarbyl with or without a substituent Q, and R5-R8 are optionally joined to form a ring or ring system; each R 12 are independently C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA non-metallic atom; each M is independently a Group VIII metal; and each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q.

[0015] In some embodiments of this subaspect, R1 and R2 are independently selected from the group consisting of C1-C20 alkyl, with or without substituent Q, and C6-C20 aryl, with or without substituent Q. Preferably, R1 and / or R2 have the formula A:

[0016] [ka]

[0017] In the formula, R 1 ~R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q; R 1 ~R 5 are optionally joined to form a ring or ring system. Preferably, R 1 ~R 5are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q.

[0018] In some embodiments of this subaspect, in said diimine metal complex, each M is independently selected from the group consisting of nickel and palladium.

[0019] In some embodiments of this subaspect, in said diimine metal complex, each Y is independently selected from the group consisting of O and S.

[0020] In some embodiments of this subaspect, in the diimine metal complex, each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without substituent Q, and C1-C10 alkoxy with or without substituent Q, and preferably selected from the group consisting of halogen, C1-C6 alkyl with or without substituent Q, and C1-C6 alkoxy with or without substituent Q.

[0021] In some embodiments of this subaspect, in the diimine metal complex, each R 12are independently C1 to C20 alkyl with or without a substituent Q, preferably C1 to C10 alkyl with or without a substituent Q, more preferably C1 to C6 alkyl with or without a substituent Q.

[0022] In some embodiments of this subaspect, in the diimine metal complex, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, preferably halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, and 3,3-dimethylbutoxy.

[0023] As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0024] In some embodiments of this subaspect, the diimine metal complex has Formula IIIb.

[0025] [ka]

[0026] In the formula, R 1 ~R 11are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q. M, X, Y, and R 12 is as defined above in the description of formula Ib.

[0027] In some preferred embodiments, in the diimine metal complex of formula IIIb, R 1 ~R 11 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q. Preferably, R 1 ~R 11are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0028] In some embodiments of this subaspect, the diimine metal complex is: 1) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = methyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 2) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = ethyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 3) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = isopropyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 4) the diimine metal complex of formula IIIb, wherein R 1 ~R 3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 5) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 6) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =F, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 7) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =Cl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 8) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =Br, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 9) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = methyl, R 2 =R 4 ~R 7=R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 10) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = ethyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 11) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = isopropyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 12) the diimine metal complex of formula IIIb, wherein R 1 ~R 3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 13) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 14) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =F, R2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 15) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =Cl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 16) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =Br, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R 12 = isobutyl, M = Ni, Y = O, X = Br; 17) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = methyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = bromomethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 18) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = ethyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = bromomethyl, R 12= ethyl, M = Ni, Y = O, X = Br; 19) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = isopropyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = bromomethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 20) the diimine metal complex of formula IIIb, wherein R 1 ~R 3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = bromomethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 21) the diimine metal complex of formula IIIb, wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = bromomethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 22) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =F, R 2 =R 4 ~R 7 =R 10 =H,R 8 =R 9 = methyl, R 11 = bromomethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 23) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =Cl, R 2 =R 4 ~R 7 =R 10 =H, R8 =R 9 = methyl, R 11 = bromomethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; 24) the diimine metal complex of formula IIIb, wherein R 1 =R 3 =Br, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = bromomethyl, R 12 = Ethyl, M = Ni, Y = O, X = Br.

[0029] In another subembodiment of the process of the present invention, the polar monomer is selected from the group consisting of olefinic monomers having one or more hydroxy groups, or the polar monomer is selected from the group consisting of olefinic monomers having one or more carboxyl groups, and the main catalyst comprises a diimine metal complex represented by formula Ic.

[0030] [ka]

[0031] In the formula, R 21 ~R 24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without the substituent Q, and C1-C20 hydrocarbyloxy with or without the substituent Q; R 21 ~R 24 are optionally joined to form a ring or ring system. R1, R2, R 11 , Y, M, and X are as defined in the description of Formula I above.

[0032] In some embodiments of this subaspect, in the diimine metal complex represented by Formula Ic, R1 and R2 are independently selected from the group consisting of C1-C20 alkyl with or without substituent Q and C6-C20 aryl with or without substituent Q. Preferably, R1 and / or R2 are groups represented by Formula A.

[0033] [ka]

[0034] In the formula, R 1 ~R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q; R 1 ~R 5 are optionally joined to form a ring or ring system. Preferably, R 1 ~R 5are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q.

[0035] In some embodiments of this subaspect, in the diimine metal complex of Formula Ic, each M is independently selected from the group consisting of nickel and palladium.

[0036] In some embodiments of this subaspect, in the diimine metal complex represented by formula Ic, each Y is independently selected from the group consisting of O and S.

[0037] In some embodiments of this subaspect, in the diimine metal complex represented by Formula Ic, each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without substituent Q, and C1-C10 alkoxy with or without substituent Q, and preferably selected from the group consisting of halogen, C1-C6 alkyl with or without substituent Q, and C1-C6 alkoxy with or without substituent Q.

[0038] In some embodiments of this subaspect, in the diimine metal complex of formula Ic, each R 11are independently C1 to C20 alkyl with or without a substituent Q, preferably C1 to C10 alkyl with or without a substituent Q, more preferably C1 to C6 alkyl with or without a substituent Q.

[0039] In some embodiments of this subaspect, in the diimine metal complex represented by Formula Ic, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, and preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy and 3,3-dimethylbutoxy.

[0040] In some embodiments of this subaspect, the diimine metal complex has a structure according to Formula IIIc.

[0041] [ka]

[0042] In the formula, R 1 ~R 10 , R 21 ~R 24are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q. 1 ~R 10 are optionally joined to form a ring or ring system, and R 21 ~R 24 are optionally joined to form a ring or ring system. 11 , Y, M, and X are as defined above in the description of formula Ic.

[0043] In some embodiments of this subaspect, in the diimine metal complex of formula IIIc, R 1 ~R 10 , R 21 ~R 24are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q. Preferably, R 1 ~R 10 , R 21 ~R 24 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0044] In some embodiments of this subaspect, the diimine metal complex has a structure represented by Formula IIc.

[0045] [ka]

[0046] where R 31 ~R 34 is R in formula Ic 21 ~R 24 and preferably R 33 and R 34 is hydrogen and R 11, Y, M and X are as defined above in the description of formula Ic.

[0047] In some embodiments, in formula R 31 ~R 34 are each independently selected from the group consisting of hydrogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, C7-C20 alkaryloxy with or without a substituent Q, and halogen. Preferably, R 31 ~R 34 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q. More preferably, R 31 ~R 34are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0048] In some embodiments of this subaspect, the diimine metal complex is: 1) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 2) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 3) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 4) the complex of formula IIIc, wherein R1 ~R 6 = methyl, R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 5) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 6) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 7) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 8) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5=R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 9) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 10) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 11) the complex of formula IIIc, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 12) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 13) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 14) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 15) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 16) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 17) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 18) the complex of formula IIIc, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 19) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 20) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = Ethyl, M = Ni, Y = O, X = Br; 21) The complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 22) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 23) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 24) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R11 = isobutyl, M = Ni, Y = O, X = Br; 25) the complex of formula IIIc, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 26) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 27) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = isobutyl, M = Ni, Y = O, X = Br; 28) the complex of formula IIIc, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R 23 =R 24 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br;

[0049] [ka]

[0050] 29) The complex represented by formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 30) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 31) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 32) the complex of formula (IIIc'), wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 33) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4=R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 34) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 35) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = ethyl, M = Ni, Y = O, X = Br; 36) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br; 37) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11= isobutyl, M=Ni, Y=O, X=Br; 38) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br; 39) the complex of formula (IIIc'), wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 31 =R 32 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br; 40) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br; 41) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br; 42) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 31 =R32 =H, R 11 = isobutyl, M=Ni, Y=O, X=Br; 43) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =HR 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 44) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 45) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 46) the complex of formula (IIIc'), wherein R 1 ~R 6 = methyl, R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 47) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 48) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 49) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 50) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, M = Ni, Y = O, X = Br; 51) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R 11 = isobutyl, M=Ni, Y=O, X=Br; 52) the complex of formula (IIIc'), wherein R 1 =R3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R 11 = isobutyl, M=Ni, Y=O, X=Br; 53) the complex of formula (IIIc'), wherein R 1 ~R 6 = methyl, R 7 ~R 10 =H, R 31 =R 32 = ethyl, R 11 = isobutyl, M=Ni, Y=O, X=Br; 54) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R 11 = isobutyl, M=Ni, Y=O, X=Br; 55) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R 11 = isobutyl, M=Ni, Y=O, X=Br; 56) the complex of formula (IIIc'), wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R 11= isobutyl, M=Ni, Y=O, X=Br.

[0051] In another subembodiment of the process of the present invention, the polar monomer is selected from the group consisting of olefinic monomers having one or more hydroxy groups, or the polar monomer is selected from the group consisting of olefinic monomers having one or more carboxy groups, and the main catalyst comprises an amino-imine metal complex represented by formula I'.

[0052] In some embodiments of this subaspect, in the amino-imine metal complex, R1 and R2 are independently selected from the group consisting of C1-C20 alkyl with or without substituent Q and C6-C20 aryl with or without substituent Q. Preferably, R1 and / or R2 are a group represented by formula A.

[0053] [ka]

[0054] In the formula, R 1 ~R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q; R 1 ~R 5are optionally joined to form a ring or ring system. Preferably, R 1 ~R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q.

[0055] In some embodiments of this subaspect, in said amino-imine metal complex, each M is independently selected from the group consisting of nickel and palladium.

[0056] In some embodiments of this subaspect, in said amino-imine metal complex, each Y is independently selected from the group consisting of O and S.

[0057] In some embodiments of this subaspect, in the amino-imine metal complex, each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without substituent Q, and C1-C10 alkoxy with or without substituent Q, preferably selected from the group consisting of halogen, C1-C6 alkyl with or without substituent Q, and C1-C6 alkoxy with or without substituent Q.

[0058] In some embodiments of this subaspect, in the amino-imine metal complex, each R 12are independently C1 to C20 alkyl with or without a substituent Q, preferably C1 to C10 alkyl with or without a substituent Q, more preferably C1 to C6 alkyl with or without a substituent Q.

[0059] In some embodiments of this subaspect, in the amino-imine metal complex, each R3 is independently selected from the group consisting of C1-C20 alkyl with or without substituent Q, C6-C20 aryl with or without substituent Q, C7-C20 aralkyl with or without substituent Q, and C7-C20 alkaryl with or without substituent Q. Preferably, each R3 is independently selected from the group consisting of C1-C10 alkyl with or without substituent Q, C6-C10 aryl with or without substituent Q, C7-C15 aralkyl with or without substituent Q, and C7-C15 alkaryl with or without substituent Q. More preferably, each R3 is C1-C6 alkyl with or without substituent Q.

[0060] In some embodiments of this subaspect, in the amino-imine metal complex, the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, preferably halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, and 3,3-dimethylbutoxy.

[0061] In some embodiments of this subaspect, the amino-imine metal complex has formula III'.

[0062] [ka]

[0063] In the formula, R 1 ~R 11 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1 to C20 alkyl with or without a substituent Q, C2 to C20 alkenyl with or without a substituent Q, C2 to C20 alkynyl with or without a substituent Q, C1 to C20 alkoxy with or without a substituent Q, C2 to C20 alkenoxy with or without a substituent Q, C2 to C20 alkynoxy with or without a substituent Q, C6 to C20 aryl with or without a substituent Q, C6 to C20 aryloxy with or without a substituent Q, C7 to C20 aralkyl with or without a substituent Q, C7 to C20 aralkyloxy with or without a substituent Q, C7 to C20 alkaryl with or without a substituent Q, and C7 to C20 alkaryloxy with or without a substituent Q. 12 , Y, M, and X are as defined above in the description of formula I'.

[0064] In some embodiments of this subaspect, in said amino-imine metal complex of formula III′, R 1 ~R 11are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q. Preferably, R 1 ~R 11 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0065] In some embodiments of this subaspect, the amino-imine metal complex is that of formula III′, wherein R 1 =R 3 = isopropyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = methyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = isopropyl, R 2 =R 4 =R5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = methyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = ethyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = methyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = ethyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = methyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = methyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 =R 5 =R 6 =R 7 =R10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = methyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = isopropyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = isopropyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = ethyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = ethyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = i-Pr, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 ~R 3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 ~R3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 =R3=CH3, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 =F, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 =Cl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12= ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 =Br, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = ethyl, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 = ethyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 = isopropyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 ~R 3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11=CH3, R3=CH3, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = methyl, R3 = isopropyl, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 =F, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = isopropyl, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 =Cl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = isopropyl, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 =Br, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =R 11 = CH3, R3 = isopropyl, R 12 = isobutyl, M=Ni, Y=O, X=Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =R 4 ~R 7 =R10 =H, R 8 =R 9 =CH3, R 11 = bromomethyl, R = isopropyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = ethyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =CH3, R 11 = CH2Br, R3 = isopropyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = isopropyl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 =CH3, R 11 = CH2Br, R3 = ethyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 ~R 3 = methyl, R 4 ~R 7 =R 10 =H, R 8 =R 9 =CH3, R 11 =CH2Br, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 = methyl, R 2 =Br, R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R = ethyl, R 11 =CH2Br, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R1 =R 3 =F, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = CH2Br, R3 = isobutyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 =Cl, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = CH2Br, R3 = isobutyl, R 12 = ethyl, M = Ni, Y = O, X = Br; said complex of formula III', wherein R 1 =R 3 =Br, R 2 =R 4 ~R 7 =R 10 =H, R 8 =R 9 = methyl, R 11 = CH2Br, R3 = isobutyl, R 12 = Ethyl, M = Ni, Y = O, X = Br.

[0066] In some embodiments of this subaspect, the amino-imine metal complex has a structure according to formula IV'.

[0067] [ka]

[0068] wherein R1 and R2 are each independently a C1 to C30 hydrocarbyl with or without a substituent Q; R 21 ~R 24are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without the substituent Q, and C1-C20 hydrocarbyloxy with or without the substituent Q; R 21 ~R 24 are optionally joined to form a ring or ring system, preferably a substituted or unsubstituted benzene ring; each R5 is independently selected from the group consisting of hydrogen and C1-C20 hydrocarbyl, with or without the substituent Q; each R 11 are independently C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA non-metal atom; each M is independently a Group VIII metal; and each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q.

[0069] The term "substituted" as used herein refers to substitution, for example, with a substituent Q.

[0070] In some embodiments of this subaspect, in the amino-imine metal complex of Formula IV', R1 and R2 are independently selected from the group consisting of C1-C20 alkyl with or without substituent Q and C6-C20 aryl with or without substituent Q. Preferably, R1 and / or R2 are groups of Formula A.

[0071] [ka]

[0072] In the formula, R 1 ~R 5are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q; R 1 ~R 5 are optionally joined to form a ring or ring system. Preferably, R 1 ~R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q. More preferably, R 1 ~R 5are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C6 alkyl with or without a substituent Q, C2-C6 alkenyl with or without a substituent Q, C2-C6 alkynyl with or without a substituent Q, C1-C6 alkoxy with or without a substituent Q, C2-C6 alkenyloxy with or without a substituent Q, C2-C6 alkynyloxy with or without a substituent Q, C6-C10 aryl with or without a substituent Q, C7-C10 aralkyl group with or without a substituent Q, C7-C10 alkaryl with or without a substituent Q, C6-C10 aryloxy with or without a substituent Q, C7-C10 aralkyloxy with or without a substituent Q, and C7-C10 alkaryloxy with or without a substituent Q.

[0073] In some embodiments of this subaspect, in said amino-imine metal complex of formula IV', each M is independently selected from the group consisting of nickel and palladium.

[0074] In some embodiments of this subaspect, in said amino-imine metal complex of formula IV′, each Y is independently selected from the group consisting of O and S.

[0075] In some embodiments of this subaspect, in the amino-imine metal complex of formula IV', each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without substituent Q, and C1-C10 alkoxy with or without substituent Q, and preferably selected from the group consisting of halogen, C1-C6 alkyl with or without substituent Q, and C1-C6 alkoxy with or without substituent Q.

[0076] In some embodiments of this subaspect, in said amino-imine metal complex of formula IV′, each R 11are independently C1 to C20 alkyl with or without a substituent Q, preferably C1 to C10 alkyl with or without a substituent Q, and more preferably C1 to C6 alkyl with or without a substituent Q.

[0077] In some embodiments of this subaspect, in the amino-imine metal complex of Formula IV', each R5 is independently selected from the group consisting of C1-C20 alkyl with or without substituent Q, C6-C20 aryl with or without substituent Q, C7-C20 aralkyl with or without substituent Q, and C7-C20 alkaryl with or without substituent Q. Preferably, each R5 is independently selected from the group consisting of C1-C10 alkyl with or without substituent Q, C6-C10 aryl with or without substituent Q, C7-C15 aralkyl with or without substituent Q, and C7-C15 alkaryl with or without substituent Q. More preferably, each R5 is C1-C6 alkyl with or without substituent Q.

[0078] In some embodiments of this subaspect, in the amino-imine metal complex of Formula IV', the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy, preferably halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy. Preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl. Preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy, and 3,3-dimethylbutoxy.

[0079] In some embodiments of this subaspect, in said amino-imine metal complex of formula IV′, R 21 ~R 24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q, and C7-C20 alkaryloxy with or without a substituent Q; 21 ~R 24 are optionally joined to form a ring or ring system. Preferably, R 21 ~R 24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, and C7-C15 alkaryloxy with or without a substituent Q. More preferably, R 21 ~R 24are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen, and more preferably selected from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

[0080] In some embodiments of this subaspect, the amino-imine metal complex has a structure represented by Formula IV'a.

[0081] [ka]

[0082] In the formula, R 31 ~R 34 is R in formula IV' 21 ~R 24 and preferably R 33 and R 34 is hydrogen, and R1, R2, R5, R 11 , Y, M and X are as defined above for formula IV'.

[0083] In some embodiments of this subaspect, the amino-imine metal complex has the following formula V or V':

[0084] [ka]

[0085] [ka]

[0086] wherein each symbol is as defined above. Preferably, the amino-imine metal complex is: 1) the complex represented by formula V, wherein R 1 =R 3 =R 4 =R6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 2) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 3) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 4) the complex of formula V, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 5) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 6) the complex of formula V, wherein R 1 =R3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 7) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 8) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 9) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 10) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22=H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 11) the complex of formula V, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 21 =R 22 =H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 12) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 13) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 14) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=R 11 = ethyl, M = Ni, Y = O, X = Br; 15) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 16) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 17) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 18) the complex of formula V, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 19) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 20) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 21) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 21 =R 22 =H, R5=CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 22) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 23) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 24) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11= ethyl, M = Ni, Y = O, X = Br; 25) the complex of formula V, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 26) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 27) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = Ethyl, M = Ni, Y = O, X = Br; 28) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 29) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 30) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 31) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 32) the complex of formula V, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 33) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 34) the complex of formula V, wherein R 1 =R 3 =R4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M = Ni, Y = O, X = Br; 35) the complex of formula V, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 22 =H, R 21 = t-butyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 36) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 37) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 38) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R32 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 39) the complex of formula V', wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 40) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 41) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = ethyl, M = Ni, Y = O, X = Br; 42) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = Ethyl, M = Ni, Y = O, X = Br; 43) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 44) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 45) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 46) the complex of formula V′, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 47) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 48) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 =Cl, R2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 49) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R5=CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 50) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =HR 31 =R 32 =R 11 = ethyl, R = CH3, M = Ni, Y = O, X = Br; 51) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, R = CH3, M = Ni, Y = O, X = Br; 52) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11= ethyl, R = CH, M = Ni, Y = O, X = Br; 53) the complex of formula V', wherein R 1 ~R 6 = methyl, R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, R = CH3, M = Ni, Y = O, X = Br; 54) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, R = CH3, M = Ni, Y = O, X = Br; 55) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 =Cl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, R = CH, M = Ni, Y = O, X = Br; 56) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 =R 11 = ethyl, R = CH, M = Ni, Y = O, X = Br; 57) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = isopropyl, R 2 =R 5 =R 7 ~R 10 =H, R31 =R 32 =R 11 = ethyl, R = CH, M = Ni, Y = O, X = Br; 58) the complex of formula V', wherein R 1 =R 3 =R 4 =R 6 = ethyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 59) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 = methyl, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 60) the complex of formula V′, wherein R 1 ~R 6 = methyl, R 7 ~R 10 =H, R 31 =R 32 = ethyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 61) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 =Br, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 62) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 =Cl, R2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; 63) the complex of formula V′, wherein R 1 =R 3 =R 4 =R 6 =F, R 2 =R 5 =R 7 ~R 10 =H, R 31 =R 32 = ethyl, R5 = CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br.

[0087] In some embodiments of the present invention, the polar monomer is one or more olefinic alcohols represented by formula G:

[0088] [ka]

[0089] wherein L1 to L3 are each independently selected from the group consisting of H and C1 to C30 alkyl, optionally with a pendant group; and L4 is a C1 to C30 alkyl, optionally with a pendant group. 30 Preferably, L4 is a C1-C alkylene having a pendant group. 30 It is alkylene.

[0090] In some embodiments of the present invention, the content of the monomer units derived from the olefinic alcohol represented by formula G in the copolymer is 0.4 to 10.0 mol % based on the total amount of the monomer units.

[0091] In some embodiments of the present invention, the polar monomer is one or more unsaturated carboxylic acids represented by formula G'.

[0092] [ka]

[0093] wherein L1 to L3 are each independently selected from the group consisting of H and C1 to C30 alkyl, optionally with a pendant group; and L4 is a C1-C 30 Preferably, L4 is a C1-C alkylene having a pendant group. 30 It is alkylene.

[0094] In some embodiments of the present invention, the content of the monomer units derived from the unsaturated carboxylic acid represented by formula G' in the copolymer is 0.2 to 15.0 mol %, more preferably 0.7 to 10.0 mol %, based on the total amount of the monomer units.

[0095] In some embodiments of the present invention, L1 and L2 are H in Formula G or Formula G'.

[0096] In some embodiments of the present invention, in Formula G or Formula G′, L3 is H or C1-C 30 alkyl, preferably H or C-C 20 alkyl, more preferably H or C-C 10 It is alkyl.

[0097] In some embodiments of the present invention, in Formula G or Formula G′, L4 is a C1-C 30 alkylene, preferably C-C, optionally with pendant groups 20 alkylene, more preferably C-C optionally with pendant groups. 10 It is preferably alkylene, more preferably C1-C6 alkylene, optionally having a pendant group.

[0098] In some embodiments of the present invention, the optional substituents of L1-L3 are halogen, C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 10It is selected from the group consisting of aryl, cyano, and hydroxy, and more preferably selected from the group consisting of C1-C6 alkyl, halogen, and C1-C6 alkoxy.

[0099] In some embodiments of the present invention, any pendant group in L4 is selected from the group consisting of halogen, C6-C 20 Aryl, C1-C 20 Alkyl and C1-C 20 Alkoxy, C6-C 20 Aryl, C1-C 20 Alkyl and C1-C 20 The alkoxy is optionally substituted by a substituent, which is preferably a halogen, a C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 10 Preferably, any pendant group in L4 is selected from the group consisting of halogen, C6-C 20 Aryl, C1-C 20 Alkyl, hydroxy substituted C1-C 20 Alkyl and alkoxy substituted C1-C 20 More preferably, the optional pendant groups are selected from the group consisting of halogen, C6-C 20 Aryl, C1-C 10 Alkyl, hydroxy substituted C1-C 10 Alkyl and alkoxy substituted C1-C 10 Preferably, the optional pendant group is selected from the group consisting of halogen, phenyl, C1-C6 alkyl, and hydroxy-substituted C1-C6 alkyl. Examples of C1-C6 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, and hexyl.

[0100] According to a preferred embodiment of the present invention, in formula G or formula G′, L1 and L2 are H; L3 is H or C1-C 30 L4 is a C1-C 30alkylene; C1-C 30 The alkyl is optionally substituted by a substituent, which is preferably halogen, C-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 10 It is selected from the group consisting of aryl, cyano and hydroxy.

[0101] According to a preferred embodiment of the present invention, in formula G or formula G′, L1 and L2 are H, L3 is H, C1-C 10 Alkyl or halogen substituted C1-C 10 alkyl, preferably L3 is H or C1-C 10 L4 is a C1-C alkyl group optionally having a pendant group. 20 alkylene, for example, L4 can be a methylene group having a pendant group, an ethylene group having a pendant group, a propylene group having a pendant group, a butylene group having a pendant group, a C5 alkylene group having a pendant group, a C6 alkylene group having a pendant group, a C7 alkylene group having a pendant group, a C8 alkylene group having a pendant group, a C9 alkylene group, and a C 10 Alkylene, C with pendant groups 12 Alkylene, C with pendant groups 14 Alkylene, C with pendant groups 18 Alkylene, C with pendant groups 20 alkylene, preferably C-C with pendant groups 10 It is alkylene.

[0102] According to a preferred embodiment of the present invention, in formula G or G′, L1 and L2 are H, and L3 is H or C 1-6 L4 is an alkyl having a pendant group 10 It is alkylene.

[0103] In the present invention, the carbon number n of a Cn alkylene group refers to the number of C atoms in the linear chain, excluding the number of C atoms in the pendant group. For example, isopropylidene (-CH2-CH(CH3)-) refers to a C2 alkylene group having a pendant group (methyl).

[0104] According to a preferred embodiment of the present invention, specific examples of the olefinic alcohol represented by formula G include 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1,1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2,2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2,4-dimethyl-4-penten-2-ol, 4-penten-2-ol, 4-methyl-4-penten-2-ol, 2-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-2-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-2-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-3-ol, 2-phenyl-4-penten-3-ol, 2-methyl ... -Penten-2-ol, 2-allyl-hexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2,3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy -6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2,5-dimethyl-1-hepten-4-ol, 2,6-dimethyl-7-octen-2-ol, 2-hydroxy-2,4,5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 3-methyl-3-hydroxy-7 -octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1,2-dihydroxy-7-octene, 2,6-dimethyl-2,6-dihydroxy-7-octene, 2,6-dimethyl-2,3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, 2-methyl-2-hydroxy-3,5-dichloro-7-octene, 3,Examples of suitable hydroxybenzoates include, but are not limited to, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3,5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octene-2,3-diol, and 2,6-dimethyl-7-octene-2,6-diol.

[0105] Specific examples of the unsaturated carboxylic acid represented by formula G' include 2-methyl-4-pentenoic acid, 2,3-dimethyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2,2,3-trimethyl-4-pentenoic acid, 2,3,3-trimethyl-4-pentenoic acid, 2-ethyl-3-methyl-4-pentenoic acid, 2-(2-methylpropyl)-4-pentenoic acid, 2,2-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, and 2,2,3,3-tetramethyl-4-pentenoic acid. acid, 2-methyl-5-hexenoic acid, 2-ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2,3-dimethyl-5-hexenoic acid, 2,2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2-(1-methylpropyl)-5-hexenoic acid, 2,2,3-trimethyl-5-hexenoic acid, 2,2-diethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2,3-dimethyl-6-heptenoic acid, 2,4-dimethyl -6-heptenoic acid, 2,2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic acid, 2-isopropyl-6-heptenoic acid, 2,3,4-trimethyl-6-heptenoic acid, 2-methyl-2-ethyl-6-heptenoic acid, 2-(1-methylpropyl)-6-heptenoic acid, 2,2,3-trimethyl-6-heptenoic acid, 2,2-diethyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 2,3-dimethyl-7-octenoic acid, 2,4-dimethyl-7-octenoic acid, 2, 2-Dimethyl-7-octenoic acid, 2-isopropyl-5-methyl-7-octenoic acid, 2-isopropyl-7-octenoic acid, 2,3,4-trimethyl-7-octenoic acid, 2-methyl-2-ethyl-7-octenoic acid, 2-(1-methylpropyl)-7-octenoic acid, 2,2,3-trimethyl-7-octenoic acid, 2,2-diethyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2,3-dimethyl-8-nonenoic acid, 2,4-dimethyl-8-nonenoic acid, 2,2-dimethyl-8-nonenoic acid, 2,including, but not limited to, 2 - diethyl - 8 - nonenoic acid, 2 - isopropyl - 5 - methyl - 8 - nonenoic acid, 2 - methyl - 9 - decenoic acid, 2,3 - dimethyl - 9 - decenoic acid, 2,4 - dimethyl - 9 - decenoic acid, or 2 - methyl - 10 - undecenoic acid.,

[0106] According to a preferred embodiment of the present invention, the cocatalyst is selected from the group consisting of an organoaluminum compound and / or an organoboron compound.

[0107] According to a preferred embodiment of the present invention, the organoaluminum compound is selected from the group consisting of an alkylaluminoxane and an organoaluminum compound of the general formula AlR n X 1 3-n (alkylaluminum or alkylaluminum halide). In the formula, R is H, C1 - C 20 saturated or unsaturated hydrocarbyl, or C1 - C 20 saturated or unsaturated hydrocarbyloxy, preferably C1 - C 20 alkyl, C1 - C 20 alkoxy, C7 - C 20 aralkyl, or C6 - C 20 aryl; X 1 is halogen, preferably chlorine or bromine; 0 < n ≤ 3. Specific examples of the organoaluminum compound include, but are not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri - n - hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane (MAO), and modified methylaluminoxane (MMAO). Preferably, the organoaluminum compound is methylaluminoxane (MAO).

[0108] According to a preferred embodiment of the present invention, the organic boron compound is selected from the group consisting of aromatic hydrocarbyl boron compounds and borate salts. The aromatic hydrocarbyl boron compound is preferably a substituted or unsubstituted phenylboron, more preferably tris(pentafluorophenyl)boron. The borate salt is preferably N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylcarbonium tetrakis(pentafluorophenyl)borate.

[0109] According to a preferred embodiment of the present invention, the concentration of the main catalyst in the reaction system is 0.00001 to 100 mmol / L, for example, 0.00001 mmol / L, 0.00005 mmol / L, 0.0001 mmol / L, 0.0005 mmol / L, 0.001 mmol / L, 0.005 mmol / L, 0.01 mmol / L, 0.05 mmol / L, 0.1 mmol / L, 0.3 mmol / L. L, 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 5 mmol / L, 8 mmol / L, 10 mmol / L, 20 mmol / L, 30 mmol / L, 50 mmol / L, 70 mmol / L, 80 mmol / L, 100 mmol / L, and any value therebetween, preferably 0.0001 to 1 mmol / L, more preferably 0.001 to 0.5 mmol / L.

[0110] According to a preferred embodiment of the present invention, when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to M of the main catalyst is (10 to 10 7):1. For example, the molar ratio is 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1,000:1, 2,000:1, 3,000:1, 5,000:1, 10,000:1, 100,000:1, 1,000,000:1, 10,000,000:1, and any value therebetween, preferably (10 to 100,000):1, more preferably (100-10,000):1. When the promoter is an organoboron compound, the molar ratio of boron in the promoter to M in the main catalyst is (0.1 to 1,000):1. For example, 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1,000:1, and any value therebetween, preferably (0.1 to 500:1).

[0111] According to preferred embodiments of the present invention, the olefin comprises an olefin having 2 to 16 carbon atoms. In some embodiments of the present invention, the olefin comprises ethylene or an α-olefin having 3 to 16 carbon atoms. In other embodiments of the present invention, the olefin comprises a C3-C 16 It is a cyclic olefin, preferably a 5-membered or 6-membered ring. Preferably, the olefin is ethylene or an α-olefin having 3 to 16 carbon atoms, more preferably ethylene or a C2-C 10 Alpha-olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

[0112] According to a preferred embodiment of the present invention, the concentration of the polar monomer, such as the olefinic alcohol monomer represented by Formula G or the unsaturated carboxylic acid monomer represented by Formula G', in the reaction system is 0.01 to 6,000 mmol / L, preferably 0.1 to 1,000 mmol / L, more preferably 1 to 500 mmol / L, for example, 1 mmol / L, 10 mmol / L, 20 mmol / L, 30 mmol / L, 50 mmol / L, 70 mmol / L, 90 mmol / L, 100 mmol / L, 200 mmol / L, 300 mmol / L, 400 mmol / L, 500 mmol / L, and any value therebetween.

[0113] According to a preferred embodiment of the present invention, the chain transfer agent is one or more selected from alkylaluminum, alkylmagnesium, alkylboron, and alkylzinc. Some chain transfer agents used herein, such as alkylaluminum, are also considered scavengers in the art.

[0114] According to a preferred embodiment of the present invention, the chain transfer agent is a trialkylaluminum and / or a dialkylzinc, preferably one or more selected from trimethylaluminum, triethylaluminum, triisopropylaluminum, and triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, and diethylzinc.

[0115] According to a preferred embodiment of the present invention, the molar ratio of the chain transfer agent to M in the main catalyst is (0.1-2,000):1, such as 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1,000:1, 2,000:1, and any value therebetween, preferably (10-600):1.

[0116] According to a preferred embodiment of the present invention, the polymerization is carried out in an alkane solvent, which is one or more C3-C 20Alkanes, preferably C3 to C 10 An alkane, such as one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, preferably one or more of hexane, heptane and cyclohexane.

[0117] According to a preferred embodiment of the present invention, the polar monomer is first subjected to a pretreatment to remove active hydrogen. Preferably, the above-mentioned co-catalyst or chain transfer agent is used to pre-treat the polar monomer to remove the active hydrogen. Preferably, during the pretreatment, the molar ratio of functional groups in the polar monomer, such as hydroxyl groups and / or carboxyl groups, to the co-catalyst or chain transfer agent is 10:1 to 1:10.

[0118] According to a preferred embodiment of the present invention, the reaction is carried out under anhydrous and oxygen-free conditions.

[0119] According to a preferred embodiment of the present invention, the reaction conditions include: a reaction temperature of -50°C to 50°C, preferably -20 to 50°C, and more preferably 0 to 50°C, such as 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, and any value therebetween; and / or a reaction time of 10 to 200 minutes, preferably 20 to 60 minutes. Furthermore, in the present invention, the reaction pressure is not particularly limited as long as the monomers can undergo a coordination copolymerization reaction. When the olefin is ethylene, from the viewpoints of cost reduction and simplification of the polymerization process, the ethylene pressure in the reactor is preferably 1 to 1000 atm, more preferably 1 to 200 atm, and more preferably 1 to 50 atm.

[0120] As used herein, the term "reaction system" refers to the entire system including solvent, olefin, polar monomer, catalyst, and optionally, chain transfer agent.

[0121] The present invention also provides olefin-polar monomer copolymers prepared by the methods described above, including spherical and / or spherical-like polymers.

[0122] According to a preferred embodiment of the present invention, the spherical and / or spherical-like polymer has an average particle size of 0.1 to 50.0 mm, for example, 0.1 mm, 0.5 mm, 1.0 mm, 2.0 mm, 3.0 mm, 5.0 mm, 8.0 mm, 10.0 mm, 15.0 mm, 20.0 mm, 25.0 mm, 30.0 mm, 35.0 mm, 40.0 mm, 45.0 mm, 50.0 mm, and any numerical value therebetween, preferably 0.5 to 20.0 mm.

[0123] According to a preferred embodiment of the present invention, the content of structural units derived from the olefinic alcohol represented by formula G in the olefin-olefinic alcohol copolymer is 0.4 to 30.0 mol%, for example, 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol%, and any value therebetween, preferably 0.7 to 10.0 mol%.

[0124] According to a preferred embodiment, the olefin-olefinic alcohol copolymer has a weight average molecular weight of 30,000 to 500,000, preferably 50,000 to 400,000.

[0125] According to a preferred embodiment of the present invention, the olefin-olefinic alcohol copolymer has a molecular weight distribution of 4.0 or less, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, and any value therebetween, preferably a molecular weight distribution of 1.0 to 4.0.

[0126] According to a preferred embodiment of the present invention, the content of structural units derived from the unsaturated carboxylic acid represented by Formula G' in the olefin-unsaturated carboxylic acid copolymer is 0.2 to 30.0 mol%, for example, 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol%, and any numerical value therebetween, preferably 0.7 to 10.0 mol%.

[0127] According to a preferred embodiment, the olefin-unsaturated carboxylic acid copolymer has a weight average molecular weight of 30,000 to 500,000, preferably 50,000 to 400,000.

[0128] According to a preferred embodiment of the present invention, the olefin-unsaturated carboxylic acid copolymer has a molecular weight distribution of 4.0 or less, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, and any value therebetween, and preferably has a molecular weight distribution of 1.0 to 4.0.

[0129] In the present invention, the particle size of a spherical or sphere-like polymer is considered herein to be equal to the diameter of a sphere having a volume equal to the volume of the particle.

[0130] According to another aspect of the present invention there is provided the use of an olefin-polar monomer copolymer as a polyolefin material.

[0131] In this disclosure, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12Symbols used in different general or structural formulae, such as R, R3, X, M, A, Y, etc., have the same definition in each general or structural formula, unless otherwise specified.

[0132] In the present invention, the term "alkyl" refers to a straight chain alkyl, a branched chain alkyl, or a cycloalkyl. For example, "C1-C 20 "Alkyl" is C1-C 20 Straight chain alkyl, C3-C 20 Branched chain alkyl or C3-C 20 refers to cycloalkyl. Examples of straight or branched chain alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl.

[0133] C3-C 20 Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0134] C6-C 20 Examples of aryl include, but are not limited to, phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0135] Alkenyl refers to straight chain alkenyl, branched chain alkenyl, or cycloalkenyl. For example, C2-C 20 Alkenyl is C1-C 20 Straight chain alkenyl, C3-C 20 Branched chain alkenyl, or C3-C 20 refers to cycloalkenyl. Examples of alkenyl include, but are not limited to, vinyl, allyl, and butenyl.

[0136] C7-C20 Examples of aralkyl include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-t-butyl.

[0137] C7-C 20 Alkaryl includes, but is not limited to, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and t-butylphenyl.

[0138] The method for preparing copolymers of olefins and polar monomers, such as olefinic alcohols or unsaturated carboxylic acids, provided by the present invention uses a novel catalyst containing a trinuclear metal complex, which has not been reported before. Therefore, the technical problem solved by the present invention is to provide a novel method for preparing olefin-polar monomer copolymers.

[0139] Furthermore, in the method for preparing an olefin-olefinic alcohol copolymer provided by the present invention, by selecting the reacted olefinic alcohol monomer, catalyst, and appropriate polymerization method, it is possible to directly prepare spherical and / or spherical-like polymers with good morphology without the need for subsequent processing such as granulation. The obtained polymerization product does not tend to scale in the reactor, making it easy to transport.

[0140] Furthermore, the method for preparing an olefin-olefinic alcohol copolymer provided by the present invention does not require a saponification reaction step, which simplifies the manufacturing process compared to the methods for preparing an olefin-olefinic alcohol copolymer currently used in the industry.

[0141] Furthermore, the method for preparing an olefin-unsaturated carboxylic acid copolymer provided by the present invention can directly prepare spherical and / or sphere-like polymers with good morphology by selecting an unsaturated carboxylic acid monomer, a catalyst, and an appropriate polymerization process, without requiring subsequent processing such as granulation. The resulting polymerization product does not tend to scale in the reactor, making it easy to transport. Furthermore, the method for preparing an olefin-unsaturated carboxylic acid copolymer provided by the present invention does not require a saponification reaction step, which simplifies the production process compared to the methods for preparing olefin-unsaturated carboxylic acid copolymers currently used in the industry.

[0142] DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram of the structural unit of the nickel complex Ni1 of Example 1 of the present invention (for clarity, hydrogen atoms, dichloromethane solvent molecules and atoms for symmetry manipulation are not marked).

[0143] FIG. 2 is a photograph of the spherical and / or sphere-like polymer obtained in Example 2 of the present invention.

[0144] FIG. 3 is a photograph of the olefin-unsaturated carboxylic acid polymer obtained in Example 20 of the present invention.

[0145] FIG. 4 is a photograph of the spherical and / or sphere-like polymer obtained in Example 70.

[0146] [Example] The present invention will be described in detail below in connection with the examples and drawings. However, it should be understood that the examples and drawings are only used to illustrate the present invention and do not constitute any limitation on the protection scope of the present invention. All reasonable modifications and combinations falling within the scope of the inventive idea of ​​the present invention are included in the protection scope of the present invention.

[0147] The analytical characterization equipment used in this invention is as follows: Prior to the measurement, the polymer sample is washed with a dilute acid solution to ensure that the metal content in the polymer is ≦50 ppm.

[0148] 1. Nuclear magnetic resonance apparatus for determining the structure of the complex ligand: Bruker DMX 300 (300 MHz), tetramethylsilicon (TMS) was used as the internal standard, and measurements were taken at 25°C.

[0149] 2. Analysis of the comonomer content of the polymer (content of structural units derived from olefinic alcohols represented by formula G): recorded on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer. 13 C NMR spectroscopy was performed using a 10 mm PASEX13 probe. The polymer samples were dissolved in 1,2,4-trichlorobenzene at 120 °C.

[0150] 3. Analysis of the comonomer content of the copolymer (content of structural units derived from unsaturated carboxylic acid represented by formula G'): recorded on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer. 13 C NMR spectroscopy was performed using a 10 mm PASEX13 probe, with the polymer sample dissolved in deuterated tetrachloroethane at 130 °C.

[0151] 4. Molecular weight and molecular weight distribution (PDI) of polymer (PDI = Mw / Mn): Measured on a PL-GPC220 chromatograph using trichlorobenzene as the solvent at 150 °C (standard: PS; flow rate: 1.0 mL / min; column: 3 × PL gel 10 um M1 × ED-B 300 × 7.5 nm).

[0152] 5. Activity measurement method: Gravimetric method, activity is expressed as polymer weight (g) / nickel (mol) x 2.

[0153] The structures of the complexes included in Examples 1-35 below are shown by Formula IIIb:

[0154] [ka]

[0155] Example 1 1) Preparation of ligand L1: Under a nitrogen atmosphere, 2,6-diethylaniline (2.0 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction mixture was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with aqueous sodium hydroxide solution, extracted with dichloromethane, and the combined organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was then subjected to column chromatography to obtain the yellow ligand L1. Yield: 69.2%. 1 H-NMR(CDCl3):δ6.94-6.92(m,6H,C Ar -CH3), 2.56-2.51(m, 4H, C Ar -CH3), 2.36-2.31(m, 4H, C Ar -CH3),1.82-1.78(m,4H,CH2),1.54(m,1H),1.24-1.18(m,12H),1.09(s,3H,CH3),0.94(m,6H,CH3).

[0156] 2) Preparation of complex Ni1 (represented by structural formula IIIb, where R 1 , R 3 is ethyl; R 2 , R 4 ~R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12 is ethyl; M is nickel, Y is O, and X is Br): An ethanol solution (10 mL) of 0.277 g (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 0.258 g (0.6 mmol) of the ligand L1. The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the mixture. The filter cake was filtered, washed with anhydrous diethyl ether, and dried under reduced pressure to obtain Ni1 as a brown powdery solid. Yield: 78.2%. Elemental analysis (C 64 H 90 Theoretical values ​​for Br6N4Ni3O2): C, 47.96; H, 5.66; N, 3.50; Experimental values ​​(%): C, 47.48; H, 6.00; N, 3.26.

[0157] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 18.0 mg (5.0 μmol) of Ni complex, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0158] Example 2 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 1, except that 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene and 30 mL of AlEt (1.0 mol / L hexane solution) were used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0159] FIG. 2 shows a photograph of the spherical and / or sphere-like polymers prepared in this example.

[0160] Example 3 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 2, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0161] Example 4 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 2, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was additionally added along with the catalyst. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0162] Example 5 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 4, except that twice the amount of diethyl zinc (i.e., 1.0 mL of diethyl zinc (1 mol / L hexane solution)) was used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0163] Example 6 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 1, except that 3.33 times the amount of 2-methyl-2-hydroxy-7-octene (i.e., 50 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene) and 3.33 times the amount of AlEt (i.e., 50 mL of AlEt (1.0 mol / L hexane solution)) were used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0164] Example 7 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 1, except that 6.67 times the amount of 2-methyl-2-hydroxy-7-octene (i.e., 100 mmol (17.0 mL) of 2-methyl-2-hydroxy-7-octene) and 6.67 times the amount of AlEt (i.e., 100 mL of a 1.0 mol / L hexane solution of AlEt) were used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0165] Example 8 1) Preparation of ligand L2: Under a nitrogen atmosphere, 2,6-diisopropylaniline (2.4 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction mixture was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the reaction mixture was refluxed for 6 hours. The reaction product was neutralized with aqueous sodium hydroxide solution, extracted with dichloromethane, and the combined organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was then subjected to column chromatography to obtain the yellow ligand L2. Yield: 41.3%. 1 H-NMR(300MHz,CDCl3),δ(ppm):7.06-6.81(m,6H,Ar-H),2.88(m,4H,CH(CH3)2),2.36( m,1H,),1.86(m,4H,CH2),1.24(d,24H,CH(CH3)2),0.96(s,6H,CH3),0.77(s,3H,CH3).

[0166] 2) Preparation of the complex Ni2 (represented by the structural formula IIIb, where R 1 , R 3 is isopropyl; R 2 , R 4 ~R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12 is ethyl; M is nickel, Y is O, and X is Br): An ethanol solution (10 mL) of 0.277 g (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 0.291 g (0.6 mmol) of the ligand L2. The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the mixture. The mixture was filtered to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under reduced pressure to obtain Ni2 as a brown powdery solid. Yield: 74.0%. Elemental analysis (C 72 H 106 Theoretical values ​​for Br6N4Ni3O2): C, 50.42; H, 6.23; N, 3.27; Experimental values ​​(%): C, 50.28; H, 6.42; N, 3.18.

[0167] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 28.6 mg (5.0 μmol) of Ni complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0168] Example 9 Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 8, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0169] Example 10 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 8, except that 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol was used as the comonomer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0170] Example 11 1) Preparation of the complex Ni3 (represented by the structural formula IIIb, where R 1 , R 3 is isopropyl; R 2 , R 4 ~R 7 , R 10 is hydrogen; R 8 , R 9 and R 11 is methyl; R 12 is isobutyl; M is nickel, Y is O, and X is Br): A 2-methyl-1-propanol solution (10 mL) of 0.277 g (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 0.291 g (0.6 mmol) of the ligand L2. The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the mixture. The mixture was filtered to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under reduced pressure to obtain Ni3 as a brown powdery solid. Yield: 76.0%. Elemental analysis (C 76 H 114 Theoretical values ​​for Br6N4Ni3O2): C, 51.54; H, 6.49; N, 3.16; Experimental values ​​(%): C, 51.28; H, 6.62; N, 3.19.

[0171] 2) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 38.9 mg (5.0 μmol) of Ni complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0172] Example 12 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 11, except that 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol was used as the comonomer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0173] Example 13 1) Preparation of ligand L3: Under a nitrogen atmosphere, 2,4,6-trimethylaniline (1.7 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction mixture was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with aqueous sodium hydroxide, extracted with dichloromethane, dried, concentrated, and then subjected to column chromatography to obtain the yellow ligand L3 in 62.5% yield. 1 HNMR (300 MHz, CDCl3), δ (ppm) [isomer ratio 1.2:1]: Major isomer: 6.72 (s, 4H, Ar-H), 2.26-2.13 (m, 12H, C Ar -CH3), 1.87(s, 6H, C Ar-CH3), 1.79 (m, 4H, CH2), 1.42 (m, 1H), 1.26 (s, 3H, CH3), 1.07 (s, 6H, CH3); minor isomer: 6.67 (s, 4H, Ar-H), 2.09-2.01 (m, 12H, C Ar -CH3), 1.85(s, 6H, C Ar -CH3),1.79(m,4H,CH2),1.40(m,1H),1.26(s,3H,CH3),0.94(s,6H,CH3).

[0174] 2) Preparation of the complex Ni4 (represented by the structural formula IIIb, where R 1 ~R 3 is methyl and R 4 ~R 7 and R 10 is hydrogen and R 8 , R 9 and R 11 is methyl and R 12 is ethyl, M is nickel, Y is O, and X is Br): An ethanol solution (10 mL) of 0.277 g (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 0.240 g (0.6 mmol) of ligand L3. The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the product. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under reduced pressure to obtain Ni4 as a brown powdery solid in 78.6% yield. Elemental analysis (C 60 H 82 Theoretical values ​​for Br6N4Ni3O2): C, 46.59; H, 5.34; N, 3.62; Experimental values ​​(%): C, 46.24; H, 5.67; N, 3.21.

[0175] 3) Polymerization: After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 7.7 mg (5 μmol) of complex Ni4 was added, followed by evacuation and filling with ethylene three times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 1 below.

[0176] Example 14 1) Preparation of ligand L4: Under a nitrogen atmosphere, 2,6-dimethyl-4-bromoaniline (2.45 g, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction mixture was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with aqueous sodium hydroxide, extracted with dichloromethane, dried, concentrated, and then subjected to column chromatography to obtain the yellow ligand L4 in 60.7% yield. 1 H NMR (300 MHz, CDCl3), δ (ppm) [isomer ratio 1.1:1]: major isomer: 7.05 (s, 4H, Ar-H), 2.18 (m, 12H, CAr-CH3), 1.85 (m, 4H, CH2), 1.37 (m, 1H), 1.26 (s, 3H, CH3), 1.06 (s, 6H, CH3); minor isomer: 7.02 (s, 4H, Ar-H), 2.04 (m, 12H, CAr-CH3), 1.85 (m, 4H, CH2), 1.37 (m, 1H), 1.26 (s, 3H, CH3), 0.96 (s, 6H, CH3).

[0177] 2) Preparation of the complex Ni5 (represented by the structural formula IIIb, where R 1 and R3 is methyl and R 2 is bromine and R 4 ~R 7 and R 10 is hydrogen and R 8 , R 9 and R 11 is methyl and R 12 is ethyl, M is nickel, Y is O, and X is Br): An ethanol solution (10 mL) of 0.278 g (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 0.318 g (0.6 mmol) of ligand L4. The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the product. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under reduced pressure to obtain Ni5 as a brown powdery solid in 74.1% yield. Elemental analysis (C 56 H 70 Br 10 Theoretical values ​​for N4Ni3O2): C, 37.24; H, 3.91; N, 3.10; Experimental values ​​(%): C, 37.38; H, 4.30; N, 3.03.

[0178] 3) Polymerization: After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then backfilled with N2 gas three times. 9.0 mg (5 μmol) of Ni5 complex was added, followed by evacuation and backfilling with ethylene three times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 1 below.

[0179] Example 15 1) Preparation of Ligand L5: Under a nitrogen atmosphere, 2,6-diisopropylaniline (2.30 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0 M, 12 mmol) was added dropwise at room temperature. The reaction mixture was refluxed for 2 hours, and the system was cooled to room temperature. Dione (1.225 g, 5 mmol) was added, and the system was refluxed for 6 hours. The reaction product was neutralized with aqueous sodium hydroxide, extracted with dichloromethane, dried, concentrated, and then subjected to column chromatography to obtain the yellow ligand L5 in 62.7% yield. 1 H NMR(300MHz,CDCl3),δ(ppm):7.05-6.83(m,6H,Ar-H),3.30(m,2H,CH2),2.80(m,4H, CH(CH3)2),1.55(m,1H),1.83(m,4H,CH2),1.26(d,24H,CH(CH3)2),0.99(s,6H,CH3).

[0180] 2) Preparation of the complex Ni6 (represented by the structural formula IIIb, where R 1 and R 3 is isopropyl, and R 2 , R 4 ~R 7 and R 10 is hydrogen and R 8 and R 9 is methyl and R 11 is CHBr and R 12 is ethyl, M is nickel, Y is O, and X is Br): An ethanol solution (10 mL) of 0.277 g (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 0.338 g (0.6 mmol) of ligand L5. The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the mixture. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under reduced pressure to obtain Ni6 as a brown powdery solid in 80.2% yield. Elemental analysis (C 72 H 104Theoretical values ​​for Br8N4Ni3O2): C, 46.17; H, 5.60; N, 2.99; Experimental values ​​(%): C, 46.24; H, 5.80; N, 3.13.

[0181] 3) Polymerization: After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 9.4 mg (5 μmol) of Ni6 complex was added, followed by evacuation and filling with ethylene three times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 1 below.

[0182] Example 16 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 2, except that 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution) was used instead of MAO. The results are shown in Table 1 below.

[0183] Example 17 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 18.0 mg (5.0 μmol) of Ni complex, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0184] Example 18 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 2, except that 500 mL of toluene was used instead of hexane. The results are shown in Table 1 below.

[0185] Comparative Example 1 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 1, except that 15 μmol of Comparative Catalyst A was used.

[0186] [ka]

[0187] Comparative Example 2 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 1, except that 15 μmol of Comparative Catalyst B was used.

[0188] [ka]

[0189] [Table 1]

[0190] Example 19 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 18.0 mg (5.0 μmol) of Ni complex, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0191] Example 20 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 19, except that twice the amount of 2,2-dimethyl-7-octenoic acid and twice the amount of AlEt were used. The results are shown in Table 1 below. Polymerization activity and polymer performance parameters are shown in Table 2 below.

[0192] Example 21 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0193] Example 22 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was additionally added along with the catalyst. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0194] Example 23 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 1.0 mL of diethyl zinc (1 mol / L hexane solution) was additionally added along with the catalyst. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0195] Example 24 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 19, except that 3.33 times the amount of 2,2-dimethyl-7-octenoic acid (i.e., 50 mmol (8.51 g)) and 3.33 times the amount of AlEt (i.e., 50 mL) (1.0 mol / L hexane solution) were used. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0196] Example 25 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 19, except that 6.67 times the amount of 2,2-dimethyl-7-octenoic acid (i.e., 100 mmol (17.02 g)) and 6.67 times the amount of AlEt (i.e., 100 mL) (1.0 mol / L hexane solution) were used. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0197] Example 26 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 28.6 mg (5 μmol) of Ni complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0198] Example 27 After continuous drying at 130 °C for 6 hours, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 28.6 mg (5 μmol) of Ni complex, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 350 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0199] Example 28 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 28.6 mg (5 μmol) of Ni complex, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0200] Example 29 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 8.9 mg (5 μmol) of complex Ni3 was used as the catalyst. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0201] Example 30 After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then backfilled with N2 gas three times. 7.7 mg (5 μmol) of complex Ni4 was added, followed by evacuation and backfilling with ethylene three times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 2 below.

[0202] Example 31 After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then backfilled with N2 gas three times. 9.0 mg (5 μmol) of Ni5 complex was added, followed by evacuation and backfilling with ethylene three times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 20°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 2 below.

[0203] Example 32 After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then backfilled with N2 gas three times. 9.4 mg (5 μmol) of Ni6 complex was added, followed by evacuation and backfilling with ethylene three times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 50°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 2 below.

[0204] Example 33 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution) was used instead of MAO. The results are shown in Table 2 below.

[0205] Example 34 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 30 mmol (5.53 g) of 10-undecenoic acid was used as the comonomer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

[0206] Example 35 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 2, except that 500 mL of toluene was used instead of hexane. Copolymerization activity and polymer performance parameters are shown in Table 2 below.

[0207] [Table 2]

[0208] From Table 2, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and unsaturated carboxylic acid, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 6 g mol -1 (Ni)·h -1 The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0209] The following structural formulas of the ligands and complexes are described in Examples 36-68:

[0210] [ka]

[0211] Example 36 1)Ligand L 11 (Represented by structural formula B, wherein R 1 , R 3 , R 4 and R 6 is isopropyl, and R 2 , R 5 , R 7 ~R 10 , R 21 and R 22 is hydrogen) was prepared according to the literature Organometallics, 2013, 32, 2291-2299.

[0212] 2) Complex Ni 11 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 and R 6 is isopropyl, and R 2 , R 5 , R 7 ~R 10 , R 21 and R 22 is hydrogen and R 11is ethyl, M is nickel, Y is O, and X is Br): A solution of 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) was added to 0.332 g (0.6 mmol) of the ligand L 11 The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the product. The filter cake was obtained by filtration, washed with anhydrous diethyl ether, and dried under reduced pressure to obtain Ni. 11 was obtained as a brown powdery solid in a yield of 78.2%. 84 H 98 Theoretical values ​​for Br6N4Ni3O2): C, 54.50; H, 5.34; N, 3.03; Experimental values ​​(%): C, 54.38; H, 5.72; N, 3.16.

[0213] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 15 mmol (2.5 mL), 15 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0214] Example 37 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 119.3 mg (5 μmol), 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0215] Example 38 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 37, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0216] Example 39 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 30 mmol (5.1 mL), 30 mL of AlEt (1.0 mol / L hexane solution), 0.5 mL of diethylzinc (1 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0217] Example 40 Ethylene copolymerization was carried out according to the polymerization procedure described in Example 39, except that twice the amount (1.0 mL) of diethylzinc (1 mol / L hexane solution) was used. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0218] Example 41 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol), 50 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 350 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0219] Example 42 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol), 100 mmol (17.0 mL) of 2-methyl-2-hydroxy-7-octene, 100 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0220] Example 43

[0221] [ka]

[0222] 1)Ligand L 12 (Represented by structural formula B, wherein R 1 , R 3 , R 4 and R 6 is ethyl, and R2 , R 5 , R 7 ~R 10 and R 22 is hydrogen and R 21 Compound A (wherein is tert-butyl) was prepared according to patent CN106397264 as follows: Compound A (2.7 g, 7.8 mmol) and 2,6-diethylaniline (3.0 ml, 17.4 mmol) were refluxed in 100 mL of toluene in the presence of p-toluenesulfonic acid (0.02 g) as a catalyst for 1 day, and then the solvent was filtered. The residue was dissolved in dichloromethane and then separated by overbased alumina column chromatography using petroleum ether / ethyl acetate (20:1) as the eluent. The second fraction was identified as the desired product. After removing the solvent, a yellow solid product was obtained in 81% yield. 1 H NMR (CDCl3, δ, ppm): 1.06 (t, 12 H, J = 7.0 Hz), 1.19 ppm (s, 18 H), 2.20 (dd, 8 H, J = 7.0 Hz), 4.70 (s, 2 H), 7.04 (m, 10 H), 7.13 (s, 2 H).

[0223] 2) Complex Ni 12 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 and R 6 is ethyl, and R 2 , R 5 , R 7 ~R 10 and R 22 is hydrogen and R 21 is tert-butyl, and R 11 is ethyl, M is nickel, Y is O, and X is Br): A solution of 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) was slowly added dropwise to a solution of 0.365 g (0.6 mmol) of the ligand L2 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the mixture. Filtration was performed to obtain a filter cake, which was washed with anhydrous diethyl ether and dried under reduced pressure to obtain the Ni12 was obtained as a brown powdery solid in a yield of 82.0%. 92 H 114 Theoretical values ​​for Br6N4Ni3O2): C, 56.28; H, 5.85; N, 2.85; Experimental values ​​(%): C, 56.43; H, 6.12; N, 3.08.

[0224] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 12 9.8 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 30 mmol (5.1 mL), 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0225] Example 44 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 12 9.8 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 30 mmol (8.5 mL), 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0226] Example 45 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 12 9.8 mg (5 μmol), 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0227] Example 46 1)Ligand L 13 Preparation of (represented by structural formula B, where R 1 , R 3 , R 4 and R 6 is methyl and R 2 and R 5 is bromine and R 7 ~R 10 and R 22 is hydrogen and R 21 Compound A (1.77 g, 5.1 mmol) and 2,6-diethyl-4-bromoaniline (2.3 g, 11.3 mmol) were refluxed in 100 mL of toluene in the presence of p-toluenesulfonic acid (0.02 g) as a catalyst for 1 day. The solvent was filtered, and the residue was dissolved in dichloromethane and separated by column chromatography using petroleum ether / ethyl acetate as the eluent. 13 was obtained in 78% yield as a yellow solid. 1H NMR (CDCl3, δ, ppm): 1.84 (s, 12H), 1.19 ppm (s, 18H), 4.70 (s, 2H), 7.04 (8H), 7.12 (s, 2H).

[0228] 2) Complex Ni 13 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R4 and R 6 is methyl and R 2 and R 5 is bromine and R 7 ~R 10 and R 22 is hydrogen and R 21 is tert-butyl, and R 11 is ethyl, M is nickel, Y is O, and X is Br): A solution of 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) was added to 0.426 g (0.6 mmol) of the ligand L 13 The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the product. The filter cake was obtained by filtration, washed with anhydrous diethyl ether, and dried under reduced pressure to obtain Ni. 13 was obtained as a brown powdery solid in a yield of 82.0%. 84 H 94 Br 10 Theoretical values ​​for N4Ni3O2): C, 46.56; H, 4.37; N, 2.59; Experimental values ​​(%): C, 46.43; H, 4.72; N, 2.98.

[0229] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 13 10.8 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 30 mmol (5.1 mL), 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0230] Example 47 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 13 10.8 mg (5 μmol), 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0231] Example 48 1) Complex Ni 14 Preparation of (represented by structural formula IIIc, where R 1 , R 3 , R 4 and R 6 is ethyl, and R 2 , R 5 , R 7 ~R 10 and R 22 is hydrogen and R 21 is tert-butyl, and R 11 is isobutyl, M is nickel, Y is O, and X is Br A solution of 0.277 g (0.9 mmol) of (DME)NiBr2 in 2-methyl-1-propanol (10 mL) was added to 0.365 g (0.6 mmol) of the ligand L 12 The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the product. The filter cake was obtained by filtration, washed with anhydrous diethyl ether, and dried under reduced pressure to obtain Ni. 14 was obtained as a brown powdery solid in a yield of 83.0%. 96 H 122Theoretical values ​​for Br6N4Ni3O2): C, 57.09; H, 6.09; N, 2.77; Experimental values ​​(%): C, 57.24; H, 6.32; N, 3.04.

[0232] 2) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 10.1 mg (5 μmol) of complexed Ni 14 After adding the ethylene, the autoclave was evacuated and backfilled with ethylene three times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt (1.0 mol / L hexane solution) were added to the autoclave, followed by 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 3 below.

[0233] Example 49

[0234] [ka]

[0235] 1)Ligand L 19 was prepared using compound B as raw material according to the method disclosed in patent application CN201510462932.2.

[0236] 2) Complex Ni 15 Preparation of (represented by formula IIIc', where R 1 =R 3 =R 4 =R 6 =Et, R 2 =R 5 =R 7 ~R 10 =R 31 =R 32 =H, R 11 = Et, M=Ni, Y=O, X=Br):

[0237] [ka]

[0238] A solution of 0.277 g (0.9 mmol) of (DME)NiBr2 in ethanol (10 mL) was added to 0.358 g (0.6 mmol) of the ligand L 19 The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the product. The filter cake was obtained by filtration, washed with anhydrous diethyl ether, and dried under reduced pressure to obtain Ni. 15 was obtained as a brown powdery solid in a yield of 84.3%. 92 H 90 Theoretical values ​​for Br6N4Ni3O2): C, 56.98; H, 4.68; N, 2.89; Experimental values ​​(%): C, 56.78; H, 4.62; N, 3.18.

[0239] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 9.7 mg (5 μmol) of complexed Ni 15 After adding the ethylene, the autoclave was evacuated and backfilled with ethylene three times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt (1.0 mol / L hexane solution) were added to the autoclave, followed by 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 3 below.

[0240] Example 50 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 30 mmol (5.1 mL), and 30 mL of AlEt (1.0 mol / L hexane solution) were added, followed by 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution). The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0241] Example 51 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol), 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0242] Example 52 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of toluene was added to the autoclave, and simultaneously, complex Ni 119.3 mg (5 μmol) of 2-methyl-2-hydroxy-7-octene, 30 mmol (5.1 mL), 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

[0243] [Table 3]

[0244] From Table 3, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and enol, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 6 g mol -1 (Ni)·h -1 The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0245] Example 53 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol), 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0246] Example 54 Ethylene copolymerization was carried out according to the procedure described in Example 53, except that twice the amount (30 mmol (5.10 g)) of 2,2-dimethyl-7-octenoic acid and twice the amount (30 mL) of AlEt were used. The results are shown in Table 4 below.

[0247] Example 55 Ethylene copolymerization was carried out according to the procedure described in Example 54, except that the polymerization temperature was 60° C. The results are shown in Table 4 below.

[0248] Example 56 Ethylene copolymerization was carried out according to the procedure described in Example 54, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 4 below.

[0249] Example 57 Ethylene copolymerization was carried out according to the procedure described in Example 54, except that 1.0 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 4 below.

[0250] Example 58 Ethylene copolymerization was carried out according to the procedure described in Example 53, except that 3.33 times the amount (50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times the amount (50 mL) of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 4 below.

[0251] Example 59 Ethylene copolymerization was carried out according to the procedure described in Example 53, except that 6.67 times the amount of 2,2-dimethyl-7-octenoic acid and 6.67 times the amount of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 4 below.

[0252] Example 60 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 12 9.8 mg (5 μmol), 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0253] Example 61 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 12 9.8 mg (5 μmol), 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 350 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0254] Example 62 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 129.8 mg (5 μmol), 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0255] Example 63 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 13 10.8 mg (5 μmol), 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0256] Example 64 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 10.1 mg (5 μmol) of complexed Ni 14 After adding the ethylene, the autoclave was evacuated and backfilled with ethylene three times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt (1.0 mol / L hexane solution) were added to the autoclave, followed by 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0257] Example 65 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 9.7 mg (5 μmol) of complexed Ni 15 After adding the ethylene, the autoclave was evacuated and backfilled with ethylene three times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt (1.0 mol / L hexane solution) were added to the autoclave, followed by 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 20°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 4 below.

[0258] Example 66 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni 11 9.3 mg (5 μmol), 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt (1.0 mol / L hexane solution) were added, followed by 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution). The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0259] Example 67 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously complex Ni11 9.3 mg (5 μmol), 30 mmol (5.53 g) of 10-undecenoic acid, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0260] Example 68 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of toluene was added to the autoclave, and simultaneously, complex Ni 11 9.3 mg (5 μmol), 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

[0261] [Table 4]

[0262] From Table 4, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and unsaturated carboxylic acid, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 6 g mol -1 (Ni)·h -1 The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0263] Compounds of the following structural formula are set forth in the examples below:

[0264] [ka]

[0265] Diimine Compound A21: An α-diimine compound of formula VI, wherein R 1 =R 3 =Me, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3; Diimine Compound A22: An α-diimine compound of formula VI, wherein R 1 =R 3 =iPr, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3; Ligand L21: An aminoimine compound of formula V, wherein R 1 =R 3 =Me, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3; Ligand L22: An aminoimine compound of formula V, wherein R 1 =R 3 =iPr, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R8 =R 9 =R 11 =CH3;R3=CH3; Ligand L23: An aminoimine compound of formula V, wherein R 1 =R 3 =iPr, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3;R3=Et; Complex Ni21: A complex of formula III, wherein R 1 =R 3 =Me, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3, R3=CH3, R 12 = Et, M = Ni, Y = O, X = Br; Complex Ni22: A complex of formula III, wherein R 1 =R 3 =iPr, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11 =CH3;R3=CH3, R 12 = Et, M = Ni, Y = O, X = Br; Complex Ni23: A complex of formula III, wherein R 1 =R 3 =iPr, R 2 =R 4 =R 5 =R 6 =R 7 =R 10 =H, R 8 =R 9 =R 11=CH3;R3=Et, R 12 = Et, M = Ni, Y = O, X = Br.

[0266] Example 69 1) Preparation of ligand L21: 1.5 mL of 2,6-dimethylaniline (12 mmol) was reacted with 57 mL of 1 M trimethylaluminum in toluene under reflux for 3 hours. Camphorquinone (1.05 g, 5 mmol) was then added, and the reaction mixture was refluxed for 8 hours. After cooling, the reaction was quenched with sodium hydroxide / ice water, the reaction mixture was extracted with ethyl acetate, and the organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L21 as colorless crystals in 70.2% yield. 1 HNMR δ(ppm)7.00-6.89(m,6H,Ar-H),3.57(s,1H,NH),2.18(s,6H,CAr-CH3),2.05(s,6H,CH3),1.74( m,4H,CH2),1.44(s,3H,CH3),1.35(m,1H),1.21(s,3H,CH3),1.01(s,3H,CH3),0.87(s,3H,CH3).

[0267] 2) Preparation of the complex Ni21: A solution (10 mL) of (DME)NiBr2 (277 mg, 0.9 mmol) in ethanol was added dropwise to a solution (10 mL) of ligand L21 (233 mg, 0.6 mmol) in dichloromethane. The resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 70% yield. Elemental analysis (C 58 H 82 Theoretical values ​​for Br6N4Ni3O2): C, 45.75; H, 5.43; N, 3.68; Experimental values ​​(%): C, 45.56; H, 5.83; N, 3.46.

[0268] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0269] Example 70 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0270] FIG. 4 shows a photograph of the spherical and / or sphere-like polymers prepared in this example.

[0271] Example 71 Ethylene copolymerization was carried out according to the procedure described in Example 70, except that the polymerization temperature was 60° C. The results are shown in Table 5 below.

[0272] Example 72 Ethylene copolymerization was carried out according to the procedure described in Example 70, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 5 below.

[0273] Example 73 Ethylene copolymerization was carried out according to the procedure described in Example 70, except that 1.0 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 5 below.

[0274] Example 74 Ethylene copolymerization was carried out according to the procedure described in Example 69, except that 3.33 times the amount (50 mmol (8.5 mL)) of 2-methyl-2-hydroxy-7-octene and 3.33 times the amount (50 mL) of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 5 below.

[0275] Example 75 Ethylene copolymerization was carried out according to the procedure described in Example 69, except that 6.67 times the amount of 2-methyl-2-hydroxy-7-octene and 6.67 times the amount of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 5 below.

[0276] Example 76 1) Preparation of ligand L22: A reaction flask was charged with 3.88 g (8 mmol) of α-diimine compound A22, 30 mL of toluene, and 1 M trimethylaluminum (16 mL, 16 mmol), in that order, and the contents were refluxed for 8 hours. The reaction was quenched with sodium hydroxide / ice water, extracted with ethyl acetate, and the organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L22 as colorless crystals in 84.2% yield. 1HNMR δ(ppm)7.19-7.06(m,6H,Ar-H),3.42(s,1H,NH),2.98(m,2H,CH(CH3)2),2.88(m,2H,CH(CH3)2),2.32(m,1H) ,1.81(m,4H,CH2),1.50(s,3H,CH3),1.21(m,24H,CH3),0.92(s,3H,CH3),0.75(s,3H,CH3),0.72(s,3H,CH3).

[0277] 2) Preparation of the complex Ni22: A solution (10 mL) of (DME)NiBr2 (277 mg, 0.9 mmol) in ethanol was added dropwise to a solution (10 mL) of ligand L22 (300 mg, 0.6 mmol) in dichloromethane. The resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 78% yield. Elemental analysis (C 74 H 114 Theoretical values ​​for Br6N4Ni3O2): C, 50.87; H, 6.58; N, 3.21; Experimental values ​​(%): C, 50.57; H, 6.73; N, 3.04.

[0278] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.7 mg (5 μmol) of Ni22 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0279] Example 77 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.7 mg (5 μmol) of Ni22 complex, 30 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0280] Example 78 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.7 mg (5 μmol) of Ni22 complex, 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0281] Example 79 1) Preparation of ligand L23: A reaction flask was charged with 3.88 g (8 mmol) of α-diimine compound A22, 30 mL of diethyl ether, and 2 M diethylzinc (4 mL, 8 mmol), in that order, and the contents were stirred at room temperature for 3 h. The reaction was quenched with ice water, and the reaction mixture was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L23 as colorless crystals in 52.1% yield.1 HNMR δ(ppm)7.17-7.06(m,6H,Ar-H),4.44(s,1H,NH),2.98(m,2H,CH(CH3)2),2.87(m,2H,CH(CH3)2),2.33(m,1H),1.86(m, 2H,CH2),1.81(m,4H,CH2),1.21(m,24H,CH3),1.08(t,3H,CH3),0.93(s,3H,CH3),0.75(s,3H,CH3),0.72(s,3H,CH3).

[0282] 2) Preparation of the complex Ni23: A solution of (DME)NiBr2 (277 mg, 0.9 mmol) in ethanol (10 mL) was added dropwise to a solution of ligand L23 (309 mg, 0.6 mmol) in dichloromethane (10 mL). The resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 72% yield. Elemental analysis (C 76 H 118 Theoretical values ​​for Br6N4Ni3O2): C, 51.42; H, 6.70; N, 3.16; Experimental values ​​(%): C, 51.29; H, 6.98; N, 3.04.

[0283] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.9 mg (5 μmol) of Ni23 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0284] Example 80 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.9 mg (5 μmol) of Ni23 complex, 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0285] Example 81 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave. Simultaneously, 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added, followed by 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution). The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0286] Example 82 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0287] Example 83 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of toluene was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0288] [Table 5]

[0289] From Table 5, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and enol, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 6 g mol -1 (Ni)·h -1The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0290] Example 84 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0291] Example 85 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0292] Example 86 Ethylene copolymerization was carried out according to the procedure described in Example 85, except that the polymerization temperature was 60° C. The results are shown in Table 6 below.

[0293] Example 87 Ethylene copolymerization was carried out according to the procedure described in Example 85, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 6 below.

[0294] Example 88 Ethylene copolymerization was carried out according to the procedure described in Example 85, except that 1.0 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 6 below.

[0295] Example 89 Ethylene copolymerization was carried out according to the procedure described in Example 84, except that 3.33 times the amount (50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times the amount (50 mL) of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 6 below.

[0296] Example 90 Ethylene copolymerization was carried out according to the procedure described in Example 84, except that 6.67 times the amount of 2,2-dimethyl-7-octenoic acid and 6.67 times the amount of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 6 below.

[0297] Example 91 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.7 mg (5 μmol) of Ni22 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0298] Example 92 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.7 mg (5 μmol) of Ni22 complex, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0299] Example 93 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.7 mg (5 μmol) of Ni22 complex, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0300] Example 94 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.9 mg (5 μmol) of Ni23 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0301] Example 95 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.9 mg (5 μmol) of Ni23 complex, 30 mmol (4.26 g) of 2-isopropyl-4-pentenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0302] Example 96 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave. At the same time, 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added, followed by 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution). The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0303] Example 97 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.53 g) of 10-undecenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0304] Example 98 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of toluene was added to the autoclave, and simultaneously 7.6 mg (5 μmol) of Ni21 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

[0305] [Table 6]

[0306] From Table 6, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and unsaturated carboxylic acid, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 6 g mol -1 (Ni)·h -1 The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0307] The following compounds, ligands and complexes are described in the examples below:

[0308] [ka]

[0309] Diimine Compound A31: An α-diimine compound represented by formula V, wherein R 1 =R 3 =R 4 =R 6 =CH3, R2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H; Diimine Compound A32: An α-diimine compound represented by formula V, wherein R 1 =R 3 =R 4 =R 6 =i-Pr, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H; Diimine Compound A33: An α-diimine compound represented by formula V′, wherein R 1 =R 3 =R 4 =R 6 =Me, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 31 =R 32 =H;

[0310] [ka]

[0311] Ligand L31: An aminoimine compound of formula VI, wherein R 1 =R 3 =R 4 =R 6 =CH3, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H, R5=CH3; Ligand L32: An aminoimine compound of formula VI, wherein R1 =R 3 =R 4 =R 6 =i-Pr, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H, R5=CH3; Ligand L33: An aminoimine compound of formula VI, wherein R 1 =R 3 =R 4 =R 6 =CH3, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H, R5=Et; Ligand L34: An aminoimine compound of formula VI′, wherein R 1 =R 3 =R 4 =R 6 =Me, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 31 =R 32 =H, R5=CH3;

[0312] [ka]

[0313] Complex Ni31: A complex of formula II, wherein R 1 =R 3 =R 4 =R 6 =CH3, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R22 =H, R5=CH3, R 11 = Et, M = Ni, Y = O, X = Br; Complex Ni32: A complex of formula II, wherein R 1 =R 3 =R 4 =R 6 =iPr, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H; R5 =CH3, R 11 = Et, M = Ni, Y = O, X = Br; Complex Ni33: A complex of formula II, wherein R 1 =R 3 =R 4 =R 6 =iPr, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H; R5 =CH3, R 11 = isobutyl, M=Ni, Y=O, X=Br; Complex Ni34: A complex of formula II, wherein R 1 =R 3 =R 4 =R 6 =CH3, R 2 =R 5 =R 7 =R 8 =R 9 =R 10 =R 21 =R 22 =H;R5=Et, R 11 = Et, M = Ni, Y = O, X = Br; Complex Ni35: A complex of formula II', wherein R 1 =R 3 =R 4 =R 6 =CH3, R 2 =R 5 =R 7 =R8 =R 9 =R 10 =R 31 =R 32 =H;R5=Me, R 11 = Et, M = Ni, Y = O, X = Br.

[0314] Example 99 1) Preparation of ligand L31: A reaction flask was charged with 3.52 g (8 mmol) of α-diimine compound A1, 30 ml of toluene, and 1 M trimethylaluminum (16 mL, 16 mmol), in that order, and the reaction mixture was refluxed for 8 hours. The reaction was quenched with sodium hydroxide / ice water, and the reaction mixture was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L31 as colorless crystals in 85.2% yield. 1 HNMR δ(ppm)7.23-6.88(m,14H),4.84(s,1H),4.73(s,1H),3.85(s,1H,NH),2.02(s,3H,CH3),1.87(s,6H,CH3),1.75(s,6H,CH3).

[0315] 2) Preparation of the complex Ni31: A 10 mL solution of (DME)NiBr2 (277 mg, 0.9 mmol) in ethanol was added dropwise to a 10 mL solution of ligand L31 (274 mg, 0.6 mmol) in dichloromethane, and the resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 74% yield. Elemental analysis (C 70 H 74 Theoretical values ​​for Br6N4Ni3O2): C, 50.68; H, 4.50; N, 3.38; N, 3.21; Experimental values ​​(%): C, 50.53; H, 4.73; N, 3.21.

[0316] 3) After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0317] Example 100 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0318] Example 101 Ethylene copolymerization was carried out according to the procedure described in Example 100, except that the polymerization temperature was 60° C. The results are shown in Table 7 below.

[0319] Example 102 Ethylene copolymerization was carried out according to the procedure described in Example 100, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was additionally added to the autoclave. The results are shown in Table 7 below.

[0320] Example 103 Ethylene copolymerization was carried out according to the procedure described in Example 100, except that 1.0 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 7 below.

[0321] Example 104 Ethylene copolymerization was carried out according to the procedure described in Example 99, except that 3.33 times the amount of 2-methyl-2-hydroxy-7-octene and 3.33 times the amount of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 7 below.

[0322] Example 105 Ethylene copolymerization was carried out according to the procedure described in Example 99, except that 6.67 times the amount of 2-methyl-2-hydroxy-7-octene and 6.67 times the amount of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 7 below.

[0323] Example 106 1) Preparation of ligand L32: A reaction flask was charged with 4.42 g (8 mmol) of α-diimine compound A32, 30 ml of toluene, and 1 M trimethylaluminum (16 mL, 16 mmol), in that order, and the reaction mixture was refluxed for 8 hours. The reaction was quenched with sodium hydroxide / ice water, and the reaction mixture was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L32 as colorless crystals in 76.2% yield. 1 HNMR δ(ppm)7.21-6.95(m,14H),4.96(s,1H),4.87(s,1H),3.85(s,1H,NH),2.51(m,4H,CH(CH3)2),2.02( s,3H,CH3),1.18(d,3H,CH3),1.11(d,3H,CH3),1.05(d,6H,CH3),0.98(d,6H,CH3),0.60(d,6H,CH3).

[0324] 2) Preparation of the complex Ni32: A 10 mL solution of (DME)NiBr2 (277 mg, 0.9 mmol) in ethanol was added dropwise to a 10 mL solution of ligand L2 (341 mg, 0.6 mmol) in dichloromethane. The resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 76% yield. Elemental analysis (C 86 H 106 Theoretical values ​​for Br6N4Ni3O2): C, 54.85; H, 5.67; N, 2.97; N, 3.21; Experimental values ​​(%): C, 54.61; H, 5.73; N, 3.14.

[0325] 3) Polymerization: After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.4 mg (5 μmol) of Ni32 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0326] Example 107 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.4 mg (5 μmol) of Ni32 complex, 30 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0327] Example 108 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.4 mg (5 μmol) of Ni32 complex, 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0328] Example 109 A 2-methyl-1-propanol solution (10 mL) of 277 mg (0.9 mmol) of (DME)NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) of 341 mg (0.6 mmol) of the ligand L32. The color of the solution immediately turned deep red, and a large amount of precipitate formed. The reaction mixture was stirred at room temperature for 6 hours, and then anhydrous diethyl ether was added to precipitate the mixture. The filter cake was filtered, washed with anhydrous diethyl ether, and dried under reduced pressure to obtain Ni33 as a brown powdery solid in 84.0% yield. FT-IR (KBr disc, cm -1 )2969,1677,1628,1462,1342,1109,794,760. Elemental analysis (C 90 H 114 Theoretical values ​​for Br6N4Ni3O2): C, 55.74; H, 5.92; N, 2.89; Experimental values ​​(%): C, 56.08; H, 6.12; N, 3.08.

[0329] After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.7 mg (5 μmol) of Ni33 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0330] Example 110 1) Preparation of ligand L33: A reaction flask was charged with 3.52 g (8 mmol) of α-diimine compound A31, 30 mL of diethyl ether, and 2 M diethylzinc (4 mL, 8 mmol), in that order, and the reaction mixture was stirred at room temperature for 3 hours. The reaction was quenched with ice water, and the reaction mixture was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L33 as colorless crystals in 50.1% yield. 1 HNMR δ(ppm)7.22-6.86(m,14H),4.82(s,1H),4.73(s,1H),3.85(s,1H,NH),2.04(m,2H,CH2CH3),1.89(s,6H,CH3),1.74(s,6H,CH3),0.89(t,3H,CH3).

[0331] 2) Preparation of the complex Ni34: A 10 mL ethanol solution of (DME)NiBr2 (277 mg, 0.9 mmol) was added dropwise to a 10 mL dichloromethane solution of ligand L3 (282 mg, 0.6 mmol). The resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 73% yield. Elemental analysis (C 72 H 78 Theoretical values ​​for Br6N4Ni3O2): C, 51.26; H, 4.66; N, 3.32; Experimental values ​​(%): C, 51.39; H, 4.93; N, 3.24.

[0332] 3) After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.4 mg (5 μmol) of Ni34 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0333] Example 111 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.4 mg (5 μmol) of Ni34 complex, 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0334] Example 112

[0335] [ka]

[0336] 1) Preparation of ligand L34: A reaction flask was charged with 4.32 g (8 mmol) of α-diimine compound A33, 30 ml of toluene, and 1 M trimethylaluminum (16 mL, 16 mmol), in that order, and the reaction mixture was stirred at room temperature for 3 hours. The reaction was quenched with ice water, and the reaction mixture was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography using petroleum ether / ethyl acetate as the eluent, affording ligand L34 as colorless crystals in 72.1% yield. 1 HNMR δ(ppm)7.68-7.54(m,8H),7.37(m,4H),7.11-7.04(m,6H),5.16(s,1H),5.08( s,1H),4.05(s,1H,NH),1.94(s,3H,CH3),1.89(s,6H,CH3),1.73(s,6H,CH3).

[0337] 2) Preparation of the complex Ni35: A 10 mL solution of (DME)NiBr2 (277 mg, 0.9 mmol) in ethanol was added dropwise to a 10 mL solution of ligand L34 (334 mg, 0.6 mmol) in dichloromethane, and the resulting mixture was stirred at room temperature for 6 hours to form a precipitate. After filtration, the filter cake was washed with diethyl ether and dried to give a red powdery solid in 72% yield. Elemental analysis (C 86 H 82 Theoretical values ​​for Br6N4Ni3O2): C, 55.56; H, 4.45; N, 3.01; Experimental values ​​(%): C, 55.74; H, 4.73; N, 3.14.

[0338] 3) Polymerization: After 6 hours of continuous drying at 130°C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N2 gas three times. 9.3 mg (5 μmol) of Ni35 complex was added, followed by evacuation and filling with ethylene three times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added to the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol / L toluene solution). The reaction mixture was vigorously stirred at 60°C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The results are shown in Table 7 below.

[0339] Example 113 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave. At the same time, 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt3 (1.0 mol / L hexane solution) were added, followed by 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution). The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0340] Example 114 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0341] Example 115 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of toluene was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

[0342] [Table 7]

[0343] From Table 7, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and enol, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 5 g mol -1 (Ni)·h -1The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0344] Example 116 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0345] Example 117 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0346] Example 118 Ethylene copolymerization was carried out according to the procedure described in Example 117, except that the polymerization temperature was 60° C. The results are shown in Table 8 below.

[0347] Example 119 Ethylene copolymerization was carried out according to the procedure described in Example 117, except that 0.5 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 8 below.

[0348] Example 120 Ethylene copolymerization was carried out according to the procedure described in Example 117, except that 1.0 mL of diethyl zinc (1 mol / L hexane solution) was also added to the autoclave. The results are shown in Table 8 below.

[0349] Example 121 Ethylene copolymerization was carried out according to the procedure described in Example 116, except that 3.33 times the amount (50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times the amount (50 mL) of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 8 below.

[0350] Example 122 Ethylene copolymerization was carried out according to the procedure described in Example 116, except that 6.67 times the amount of 2,2-dimethyl-7-octenoic acid and 6.67 times the amount of AlEt (1.0 mol / L hexane solution) were used. The results are shown in Table 8 below.

[0351] Example 123 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.4 mg (5 μmol) of Ni32 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0352] Example 124 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.4 mg (5 μmol) of Ni32 complex, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 60 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0353] Example 125 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.4 mg (5 μmol) of Ni32 complex, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0354] Example 126 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.7 mg (5 μmol) of Ni33 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 60 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0355] Example 127 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.4 mg (5 μmol) of Ni34 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0356] Example 128 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.4 mg (5 μmol) of Ni34 complex, 30 mmol (4.26 g) of 2-isopropyl-4-pentenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0357] Example 129 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 9.3 mg (5 μmol) of Ni35 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0358] Example 130 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 15 mL of a toluene solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (1 mmol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0359] Example 131 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of hexane was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.53 g) of 10-undecenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0360] Example 132 After 6 hours of continuous drying at 130 °C, a 1 L stainless steel polymerization autoclave equipped with a mechanical stirrer was evacuated while hot and then filled with N gas three times. 500 mL of toluene was added to the autoclave, and simultaneously 8.3 mg (5 μmol) of Ni31 complex, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), and 6.5 mL of MAO (1.53 mol / L toluene solution) were added. The reaction mixture was stirred at 30 °C for 30 minutes, and the ethylene pressure was maintained at 10 atm. Finally, the reaction mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

[0361] [Table 8]

[0362] From Table 8, it can be seen that when the catalyst of the present invention catalyzes the copolymerization of ethylene and unsaturated carboxylic acid, it exhibits higher polymerization activity and the resulting polymer has a higher molecular weight. 5 g mol -1 (Ni)·h -1The molecular weight of the polymer can be adjusted over a wide range by adding a chain transfer agent. Also, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0363] It should be noted that the above examples are used only to illustrate the present invention and do not constitute any limitation to the present invention. Although the present invention has been described with reference to exemplary examples, it should be understood that the terms used herein are descriptive and explanatory, rather than limiting. The present invention may be modified within the scope of the claims of the present invention as set forth, and may be modified without departing from the scope and spirit of the present invention. The present invention described herein relates to specific methods, materials, and embodiments, but this is not meant to limit the present invention to the specific examples disclosed herein. On the contrary, the present invention can be extended to all other methods and applications having the same functions. [Brief explanation of the drawings]

[0364] [Figure 1] FIG. 1 is a diagram of the structural unit of the nickel complex Ni1 of Example 1 of the present invention (for clarity, hydrogen atoms, dichloromethane solvent molecules and atoms for symmetry manipulation are not marked). [Figure 2] FIG. 2 is a photograph of the spherical and / or sphere-like polymer obtained in Example 2 of the present invention. [Figure 3] FIG. 3 is a photograph of the olefin-unsaturated carboxylic acid polymer obtained in Example 20 of the present invention. [Figure 4] FIG. 4 is a photograph of the spherical and / or sphere-like polymer obtained in Example 70.

Claims

[Claim 1] 1. A process for preparing an olefin-polar monomer copolymer, comprising copolymerizing an olefin and a polar monomer in the presence of a catalyst and optionally a chain transfer agent to prepare the olefin-polar monomer copolymer; The catalyst comprises a main catalyst and, optionally, a co-catalyst, and the main catalyst is a diimine-metal complex represented by Formula 1: 【Chemistry 1】 In the formula, R １ and R ２ are each independently a C1 to C30 hydrocarbyl with or without a substituent Q; R ３ and R ４ are each independently selected from the group consisting of hydrogen, halogen, hydroxy, and C1 to C20 hydrocarbyl with or without the substituent Q; ３ and R ４ groups may be optionally joined to form a ring or ring system; each R １１ are independently C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA non-metallic atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q; or an amino-imine metal complex represented by formula 1′: 【Chemistry 2】 In the formula, R １ and R ２ are each independently a C1 to C30 hydrocarbyl with or without a substituent Q; ３ is independently selected from the group consisting of hydrogen and C1 to C20 hydrocarbyl with or without the substituent Q; R ５ From R ８ are each independently selected from the group consisting of hydrogen, halogen, hydroxy, and C1 to C20 hydrocarbyl with or without the substituent Q; R ５ From R ８ The groups may be optionally joined to form a ring or ring system; each R １２ are independently C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA non-metallic atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q; Preferably, the polar monomer is a vinyl monomer having one or more hydroxy groups and / or one or more carboxy groups.

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