Preparation method and application of symmetrical camphor-based α-diimine nickel complex with high thermal stability

Abstract

The present invention provides a high thermal stability symmetrical camphoryl α-diimine nickel complex for preparing ultra-high molecular weight polyethylene and a preparation method and application thereof. The structural formula of the metal nickel complex is shown in formula (I). The metal nickel complex provided by the present invention exhibits very good catalytic activity and good thermal stability when used to catalyze ethylene polymerization. The prepared polyethylene has a weight average molecular weight M w 0.02–23.7×10 5 g mol ‑1 The molecular weight of the polyethylene elastomer fluctuates between 1 and 2, and the molecular weight distribution is narrow, ranging from 1.6 to 2.6, showing a strong control performance on the molecular weight of polyethylene. In addition, this type of symmetrical camphor-based α-diimine nickel complex can be used to prepare ultra-high molecular weight polyethylene, especially under the condition of MMAO co-catalyst, the molecular weight of the polyethylene elastomer obtained by Ni5 and Ni6 is mostly above one million, and the highest can reach 23.7×10 5 g mol ‑1 , is a type of potential high value-added polyethylene with great potential for industrial application.

Description

Technical Field

[0001] The invention relates to a high thermal stability symmetrical camphor-based alpha-diimine nickel complex for preparing ultra-high molecular weight polyethylene and a preparation method and application thereof, belonging to the field of polyolefin catalysts. Background Art

[0002] The most important material produced by the petrochemical industry is polyolefins, of which polyethylene occupies the largest market share. A variety of catalysts can promote the growth of olefin chains to obtain polyolefins or α-olefins, including complexes based on late transition metals. Most notably, the Brookhart research group first reported more than 20 years ago that α-diimine coordinated nickel and palladium complexes catalyzed ethylene polymerization (J.Am.Chem.Soc.,1995,117,6414), obtaining high molecular weight, highly branched polyethylene, whose structure is shown in Formula 1 and Formula 2:

[0003]

[0004] In addition, this type of catalyst was found to have good tolerance to functional groups / polar monomers in subsequent studies (Chem. Rev., 2009, 109, 5157). For N^N type α-diimine-nickel catalysts, the alkyl substitution pattern of the N-aryl and ligand main chains has a significant impact on the polymerization activity and polymer microstructure. This regulation of the spatial / electronic properties of the group is aimed at the ultimate synthesis of high molecular weight polyethylene materials. Among them, the nickel complex with 9,10-phenanthrenequinone-based α-diimine ligands (Formula 3) reported by the Li research group can efficiently catalyze the polymerization of ethylene to produce high molecular weight polyethylene (1.2–2.1×10 6 g mol -1 )(J.Mol.Catal.A:Chem.,2009,303,110). In addition, the complex with 4,5-bis(aromatic imide)pyrene subunit N^N-ligand (Formula 4) designed by the inventor's research group has an activity of up to 4.4×10 6 g(PE)mol -1 (Ni)h -1 The high activity of the ethylene glycol can produce polyethylene with a high degree of branching (130 branches per 1000 carbon atoms) and a narrow molecular weight distribution (Dalton Trans., 2013, 42, 9166–9175).

[0005]

[0006]

[0007] The thermal instability of α-diimine nickel catalysts is generally considered to be the main disadvantage of this type of nickel complex catalyst, which also limits its industrial application. Many research groups have been committed to designing different diimine skeletons to improve their thermal stability, such as designing ligand skeletons that can prevent axial rotation of N-aryl groups. For many years, the inventor's research group has also been committed to exploring the scope, versatility and thermal stability of nickel (II) complexes as precatalysts for ethylene polymerization (and oligomerization). We focus on adjusting the types of imine-containing multidentate nitrogen donor ligands around the metal center and their fine-tuning on the activity, thermal stability and microstructure of the catalyst itself. Among them, the inventor's research group designed a series of ligand skeletons containing ortho-blocked diphenylmethyl substituents and introduced different electron-withdrawing groups at the para position of their N-aryl (Formula 5). They all showed excellent catalytic activity and were able to form highly branched polyethylene. Nickel complexes containing p-nitro substituents can catalyze the polymerization of ethylene to produce polyethylene with a molecular weight of 10 6 g mol -1 Ultra-high molecular weight polyethylene with a narrow molecular weight distribution.

[0008]

[0009] However, the optimal catalytic temperature of the above catalyst is still limited to between 30°C and 40°C, and its thermal stability still needs to be further improved. Summary of the invention

[0010] In order to improve the problems existing in the prior art, the present invention provides a symmetrical camphoryl α-diimine nickel complex as shown in the following formula (I):

[0011]

[0012] Among them, R 1 The same or different, each independently selected from H, F, Cl, Br, I, unsubstituted or optionally substituted with one or more R a Substituted with the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy;

[0013] R 2 The same or different, each independently selected from H, F, Cl, Br, I, unsubstituted or optionally substituted with one or more R a Substituted with the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy;

[0014] R 3 Selected from H, -CH 3 、-CH 2 SO 3 H, -CH 2 SO 3 Cl, -COOH, -COOCH 3 , -C(C 6 H 5 ) 2 OH, -C(C 6 H 5 ) 2 OCH 3 , unsubstituted or optionally substituted with one or more R b Substituted with the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy, C 1-6 Alkylidene aryl;

[0015] X are the same or different and are independently selected from halogen;

[0016] Each R a may be the same or different, and are independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy;

[0017] Each R b may be the same or different, and are independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy;

[0018] Preferably, R 1 The same or different, each independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy, diphenylmethyl, di(4-fluorophenyl)methyl;

[0019] R 2 The same or different, each independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy, diphenylmethyl, di(4-fluorophenyl)methyl;

[0020] R 3 Selected from H, -CH 3 、-CH 2 SO 3 H, -CH 2 SO 3 Cl, -COOH, -COOCH 3 , -C(C 6 H 5 ) 2 OH, -C(C 6 H 5 ) 2 OCH 3 ;

[0021] X are the same or different and are independently selected from F, Cl, Br;

[0022] More preferably, R 1 The same or different, each independently selected from H, C 1-6 Alkyl, diphenylmethyl, di(4-fluorophenyl)methyl;

[0023] R 2 The same or different, each independently selected from H, C 1-6 Alkyl, diphenylmethyl, di(4-fluorophenyl)methyl;

[0024] R 3 Selected from H, CH 3 , CH 2 SO 3 Cl, COOH, C(C 6 H 5 ) 2 OCH 3 ;

[0025] X is the same or different and is independently selected from Cl and Br.

[0026] Also preferably, R1 The same or different, each independently selected from H, C 1-3 Alkyl, diphenylmethyl, di(4-fluorophenyl)methyl;

[0027] R 2 The same or different, each independently selected from H, C 1-3 Alkyl, diphenylmethyl, di(4-fluorophenyl)methyl;

[0028] R 3 Selected from H, -CH 3 , -C(C 6 H 5 ) 2 OCH 3 ;

[0029] X is the same or different and is independently selected from Cl and Br.

[0030] Still more preferably, R 1 the same or different, each independently selected from H, methyl, ethyl, isopropyl, diphenylmethyl, di(4-fluorophenyl)methyl;

[0031] R 2 the same or different, each independently selected from H, methyl, ethyl, isopropyl, diphenylmethyl, di(4-fluorophenyl)methyl;

[0032] R 3 Selected from H, CH 3 ;

[0033] X is selected from Br.

[0034] Most preferably, the nickel complex has a structure shown in the following formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5) or formula (I-6):

[0035]

[0036] As an example, the complex represented by formula (I) can be selected from complexes having the following group definitions:

[0037] C1:R 1 =Me; R 2 =H; R 3 =Me; X is Br;

[0038] C2:R 1 =H; R 2 =Me; R 3 =Me; X is Br;

[0039] C3:R 1 =Me; R 2 =Me; R3 =Me; X is Br;

[0040] C4:R 1 =Me; R 3 =Me; X is Br;

[0041] C5: R 2 =Me; R 3 =Me; X is Br;

[0042] C6: R 3 =Me; X is Br;

[0043] The present invention also provides an intermediate of a symmetrical camphoryl α-diimine nickel complex as shown in the following formula (II):

[0044]

[0045] Wherein, in formula (II), R 1 The same or different, each independently selected from H, F, Cl, Br, I, unsubstituted or optionally substituted with one or more R a Substituted with the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy;

[0046] R 2 The same or different, each independently selected from H, F, Cl, Br, I, unsubstituted or optionally substituted with one or more R a Substituted with the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy;

[0047] R 3 Selected from H, -CH 3 、-CH 2 SO 3 H, -CH 2 SO 3 Cl, -COOH, -COOCH 3 , -C(C 6 H 5 ) 2 OH, -C(C 6 H5 ) 2 OCH 3 , unsubstituted or optionally substituted with one or more R b Substituted with the following groups: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy, C 1-6 Alkylidene aryl;

[0048] R a Having the definitions as above;

[0049] R b Has the definition as above.

[0050] Preferably, R 1 The same or different, each independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy, diphenylmethyl, di(4-fluorophenyl)methyl;

[0051] R 2 The same or different, each independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, C 6-14 Aryl, C 6-14 Aryloxy, diphenylmethyl, di(4-fluorophenyl)methyl;

[0052] R 3 Selected from H, -CH 3 、-CH 2 SO 3 H, -CH 2 SO 3 Cl, -COOH, -COOCH 3 , -C(C 6 H 5 ) 2 OH, -C(C 6 H 5 ) 2 OCH 3 ;

[0053] More preferably, R 1The same or different, each independently selected from H, C 1-6 Alkyl, diphenylmethyl or di(4-fluorophenyl)methyl;

[0054] R 2 The same or different, each independently selected from H, C 1-6 Alkyl, diphenylmethyl or di(4-fluorophenyl)methyl;

[0055] R 3 Selected from H, -CH 3 、-CH 2 SO 3 Cl, -COOH, -C(C 6 H 5 ) 2 OCH 3 .

[0056] Also preferably, R 1 The same or different, each independently selected from H, C 1-3 Alkyl, diphenylmethyl or di(4-fluorophenyl)methyl;

[0057] R 2 The same or different, each independently selected from H, C 1-3 Alkyl, diphenylmethyl or di(4-fluorophenyl)methyl;

[0058] R 3 Selected from H, -CH 3 、-CH 2 SO 3 Cl, -C(C 6 H 5 ) 2 OCH 3 .

[0059] Still more preferably, R 1 are the same or different, each independently selected from H, methyl or di(4-fluorophenyl)methyl;

[0060] R 2 are the same or different, each independently selected from H, methyl or di(4-fluorophenyl)methyl;

[0061] R 3 Selected from H, -CH 3 .

[0062] Most preferably, the nickel complex intermediate has a structure shown in the following formula (II-1), formula (II-2), formula (II-3), formula (II-4), formula (II-5) or formula (II-6):

[0063]

[0064] That is, the nickel complex intermediate represented by formula (II) is selected from the complex intermediate defined by the following groups:

[0065] L1:R 1 =Me; R 2 =H; R 3 =Me;

[0066] L2:R 1 =H; R 2 =Me; R 3 =Me;

[0067] L3:R 1 =Me; R 2 =Me; R 3 =Me;

[0068] L4:R 1 =Me; R 2 =(p-FPh) 2 CH-; R 3 =Me;

[0069] L5:R 1 =(p-FPh) 2 CH-; R 2 =Me; R 3 =Me;

[0070] L6:R 1 =(p-FPh) 2 CH-; R 2 =(p-FPh) 2 CH-; R 3 =Me.

[0071] The present invention also provides a catalyst composition, which comprises a main catalyst and an optional co-catalyst, wherein the main catalyst is selected from the nickel complex represented by formula (I);

[0072] According to the present invention, the cocatalyst may be selected from one or more of aluminoxane, alkylaluminum and alkylaluminum chloride;

[0073] According to the present invention, the aluminoxane may be selected from one or both of methylaluminoxane (MAO) and triisobutylaluminum-modified methylaluminoxane (MMAO);

[0074] According to the present invention, the alkyl aluminum can be selected from trimethyl aluminum (Me 3 Al), triethylaluminum (Et 3 Al) or triisobutylaluminum ( i Bu 3 A1) one or two;

[0075] According to the present invention, the alkylaluminum chloride can be selected from ethylaluminum dichloride (AlEtCl 2 ), diethylaluminum chloride (Et 2 AlCl), dimethylaluminum chloride (Me 2 AlCl), preferably dimethylaluminum chloride (Me 2 AlCl).

[0076] According to the present invention, when the catalyst composition further includes a co-catalyst, the molar ratio of the metal Al in the co-catalyst to the central metal Ni of the nickel complex shown in formula (I) may be (100-4000):1, preferably (200-3000):1, for example, 200:1, 500:1, 1000:1, 1500:1, 2000:1 or 3000:1.

[0077] Wherein, when the co-catalyst is methylaluminoxane (MAO), the molar ratio of the metal Al in methylaluminoxane (MAO) to the central metal Ni of the nickel complex represented by formula (I) is (1000-3000):1, and the preferred molar ratio is 2000:1.

[0078] Wherein, the co-catalyst is ethylaluminum dichloride (AlEtCl 2 ) when ethylaluminum dichloride (AlEtCl 2 ) and the central metal Ni of the nickel complex represented by formula (I) is (100-1000):1, and the preferred molar ratio is 500:1.

[0079] Wherein, the co-catalyst is trimethylaluminum (AlMe 3 ) when trimethylaluminum (AlMe 3 ) and the central metal Ni of the nickel complex represented by formula (I) is (100-1000):1, and the preferred molar ratio is 500:1.

[0080] Wherein, when the co-catalyst is triisobutylaluminum-modified methylaluminoxane (MMAO), the molar ratio of metal Al in triisobutylaluminum-modified methylaluminoxane (MMAO) to the central metal Ni of the nickel complex represented by formula (I) is (500-4000):1, preferably (1000-4000):1, for example, 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 3500:1 or 4000:1;

[0081] Wherein, the co-catalyst is dimethylaluminum chloride (Me 2 AlCl), dimethylaluminum chloride (Me 2The molar ratio of the metal Al in AlCl) to the central metal Ni of the nickel complex shown in formula (I) is (200-1000):1, preferably (200-800):1, for example, it can be 200:1, 300:1, 400:1, 500:1, 600:1, 700:1 or 800:1.

[0082] According to an embodiment of the present invention, when the co-catalyst is dimethylaluminum chloride (Me 2 AlCl), dimethylaluminum chloride (Me 2 The molar ratio of the metal Al in AlCl) to the central metal Ni of the nickel complex shown in formula (I) can be (200-800):1, preferably (200-600):1, and more preferably 400:1.

[0083] When the co-catalyst is triisobutylaluminum-modified methylaluminoxane (MMAO), the molar ratio of metal Al in triisobutylaluminum-modified methylaluminoxane (MMAO) to the central metal Ni of the nickel complex represented by formula (I) can be (1000-4000):1, preferably (1000-3000):1, and further preferably 1500:1.

[0084] The present invention also provides a method for preparing the symmetrical camphoryl α-diimine nickel complex represented by the above formula (I), comprising the following steps:

[0085] The compound represented by formula (II) is reacted with a nickel-containing compound (such as a complexation reaction) to obtain a nickel complex represented by formula (I).

[0086] According to the present invention, the nickel-containing compound may be selected from nickel-containing halides, for example (DME)NiBr 2 、NiCl 2 6H 2 O or NiBr 2 , such as (DME)NiBr 2 or NiCl 2 6H 2 O.

[0087] According to the present invention, the reaction is preferably carried out under oxygen-free conditions, for example, under the protection of an inert gas such as nitrogen.

[0088] According to the present invention, the molar ratio of the nickel-containing compound to the compound represented by formula (II) can be 1:1-2, preferably 1:1-1.5; more preferably 1:1.

[0089] According to the present invention, the reaction temperature may be 0-35°C, for example, 10-30°C, such as 20-25°C; the reaction time may be 8-16 hours, preferably 12-16 hours, more preferably 14-16 hours.

[0090] According to the present invention, the reaction can be carried out in an organic solvent, and the organic solvent can be selected from one or more of halogenated alkanes or alcohol solvents, such as one or both of dichloromethane and ethanol.

[0091] Preferably, the obtained nickel complex represented by formula (I) can be further purified.

[0092] The purification method may comprise the following steps:

[0093] a) removing the solvent from the obtained compound represented by formula (I) by using a vacuum pump, and then dissolving it in an organic solvent (such as anhydrous ether);

[0094] b) After precipitation, the solid and liquid were separated, and the solid phase was washed with anhydrous ether and dried.

[0095] The present invention also provides a method for preparing a symmetrical camphoryl α-diimine nickel complex intermediate represented by formula (II), comprising the following steps:

[0096] 1) Aniline represented by formula (III) and AlMe 3 The reaction obtains a reaction solution containing a secondary amine structure connected by an aluminum bridge as shown in formula (IV);

[0097] 2) continuing to add (D, L)-camphorquinone represented by formula (V) to the reaction solution in step 1) for condensation reaction to obtain a compound represented by formula (II);

[0098]

[0099] According to the present invention, in step 1), the reaction can be carried out in a solvent, for example, in an aromatic hydrocarbon solvent, such as toluene.

[0100] According to the present invention, in step 1), the reaction is preferably carried out under heating reflux for 3-12 hours, more preferably for 5-8 hours.

[0101] According to the present invention, in step 1), the aniline and AlMe 3 The molar feed ratio can be 1 to 2:1, preferably 1:1.

[0102] According to the present invention, in step 2), the condensation reaction can be carried out in a solvent, for example, in an aromatic hydrocarbon solvent, such as toluene.

[0103] According to the present invention, in step 2), the condensation reaction can be carried out under heating reflux for 6-24 hours, preferably 10-24 hours.

[0104] According to the present invention, in step 2), the molar feed ratio of the (D,L)-camphorquinone represented by formula (V) to the aniline in step 1) can be 4 to 6:12, preferably 5:12.

[0105] According to the present invention, preferably, the obtained compound represented by formula (II) can be further purified.

[0106] The purification method may include the following steps:

[0107] a') dissolving the compound represented by formula (II) obtained in step 2) in dichloromethane;

[0108] b') using basic alumina for loading, performing column chromatography on a basic alumina column, using a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of petroleum ether to ethyl acetate is preferably 50:1) as an eluent for elution, detecting the eluted fraction by thin layer chromatography, and collecting a second fraction;

[0109] c') removing the solvent to obtain a purified compound represented by formula (II).

[0110] The use of the symmetrical camphoryl α-diimine nickel complex represented by formula (I) or a catalyst composition containing the symmetrical camphoryl α-diimine nickel complex represented by formula (I) in catalyzing olefin polymerization is preferably used for catalyzing ethylene polymerization.

[0111] The present invention also provides a method for preparing polyethylene, comprising subjecting ethylene to polymerization reaction under the action of the catalyst composition as described above to obtain polyethylene.

[0112] Preferably, the polymerization reaction temperature is 30 to 90°C, for example, 20°C, 30°C or 80°C;

[0113] The polymerization reaction time is 5 to 120 min, for example, 5 min, 10 min, 15 min, 45 min, 60 min or 120 min; the polymerization reaction pressure is 0.5 to 10 atm, for example, 5 atm or 10 atm.

[0114] According to the present invention, the polymerization reaction can be carried out in a solvent, and the solvent can be selected from one or more of toluene, dichloromethane, ethanol, tetrahydrofuran, hexane or cyclohexane.

[0115] According to the present invention, the polymerization reaction is preferably carried out under ethylene atmosphere.

[0116] The weight average molecular weight of the obtained polyethylene can be 0.02–23.7×10 5 g·mol -1 , up to 23.7×10 5 gmol -1 The molecular weight distribution is narrow, ranging from 1.6 to 2.6, and the degree of branching can be 19-149 / 1000C.

[0117] Definitions and Explanations of Terms

[0118] The term "C 1-6 “Alkyl” is understood as meaning a linear or branched, saturated, monovalent hydrocarbon radical having 1, 2, 3, 4, 5 or 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl or their isomers. In particular, the radicals have 1, 2, 3 or 4 carbon atoms (“C 1-4 alkyl), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly, the radical having 1, 2 or 3 carbon atoms (“C 1-3 alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0119] The term "C 3-10 "Cycloalkyl" is understood to mean a saturated, monovalent, monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10 The cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.

[0120] The term "C 6-14 The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 Aryl), especially a ring having 6 carbon atoms ("C 6 aryl), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 "aryl"), for example anthracenyl.

[0121] The term "halogen" includes F, Cl, Br, I.

[0122] The beneficial effects of the present invention are:

[0123] 1. Symmetrical camphoryl α-diimine nickel complexes and intermediates thereof provided by the present invention. Such nickel complexes have a single catalytic active center and can achieve the molecular weight of the polymer (0.02–23.7×10 5 g·mol -1 ) and branching degree (19–149 / 1000C), and has the advantages of high catalytic activity, low cost and good thermal stability.

[0124] 2. The present invention provides a method for preparing a symmetrical camphoryl α-diimine nickel complex and an intermediate thereof. The two preparation methods have the advantages of mild reaction conditions, short cycle, simple operation conditions, etc.

[0125] 3. The metal nickel complex provided by the present invention exhibits very good catalytic activity and good thermal stability when used to catalyze ethylene polymerization. The use of the symmetrical camphoryl α-diimine nickel complex and its intermediate provided by the present invention, the nickel complex is used as a catalyst for ethylene polymerization, not only has high catalytic activity, but also has good thermal stability. For example, under the condition of high temperature 80 degrees Celsius, Me 2 Under AlCl conditions, the activity of nickel complexes in catalyzing ethylene polymerization can reach as high as 11.2×10 6 gPE mol -1 (Ni)h -1 Even at 90°C, the complex can still maintain good activity, 4.6×10 6 g PE mol -1 (Ni)h -1 The weight average molecular weight of the polyethylene prepared is M w 0.02–23.7×10 5 g mol -1 The molecular weight distribution of Ni5 and Ni6 fluctuates between 1 and 2.6, and the molecular weight distribution is narrow, ranging from 1.6 to 2.6, showing a strong control performance on the molecular weight of polyethylene. In addition, this type of symmetrical camphor-based α-diimine nickel complex can be used to prepare ultra-high molecular weight polyethylene, especially under the condition of MMAO co-catalyst, the molecular weight of polyethylene elastomers obtained by Ni5 and Ni6 is mostly above one million, and the highest can reach 23.7×10 5g mol -1 , is a type of potential high value-added polyethylene with great potential for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0126] Figure 1 Schematic diagram of the crystal structure of complex L5.

[0127] Figure 2 Schematic diagram of the crystal structure of complex C6.

[0128] Figure 3 This is the temperature-increasing NMR carbon spectrum of the polymer obtained in Example 16i.

[0129] Figure 4 This is the temperature-increasing NMR carbon spectrum of the polymer obtained in Example 22j. DETAILED DESCRIPTION

[0130] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0131] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0132] Unless otherwise specified, the concentrations in the following examples are molar concentrations.

[0133] The molecular weight and molecular weight distribution of the polymers obtained in the following ethylene polymerization examples are measured by conventional high temperature GPC methods, the melting points are measured by conventional DSC methods, and the polymerization activities of the polymers are calculated according to the following formula: polymerization activity = polymer yield / (catalyst dosage·polymerization time). The calculation method of the degree of branching can be found in the literature (Macromolecules, 1999, 32, 1620-1625; Polym., J. 1984, 16, 731-738).

[0134] All the synthesized compounds described below were confirmed by NMR, IR and elemental analysis.

[0135] As a preferred embodiment, the synthesis of the complex in the following examples is carried out according to the following reaction equation:

[0136]

[0137] Example 1

[0138] Preparation of (1R, 3E, 4R)-N 2 , N 3 Bis(2,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide [L1], wherein R 1 is methyl, R2 For hydrogen.

[0139] Under nitrogen atmosphere, 2,6-dimethylaniline (0.73 g, 6 mmol) dissolved in toluene (20 mL) was injected into a Schlenk flask, trimethylaluminum (3 mL, 2.0 mol / L dissolved in n-hexane) was slowly added to the reaction solution with a syringe at room temperature, and then the reaction mixture was heated to reflux for 4 h. After the solution was cooled to room temperature, (D,L)-camphorquinone (0.42 g, 2.5 mmol) was added to the reaction solution, and the reflux reaction was continued for 10 h. After the reaction solution was cooled to 0 ° C, 5% NaOH aqueous solution was added dropwise to slowly hydrolyze the remaining AlMe 3 . Afterwards, the reaction solution was extracted with ethyl acetate, and the crude product was obtained after the solvent was dried by spin drying. The crude product was further purified by basic alumina column chromatography (40 / 1, petroleum ether / ethyl acetate). The eluted fraction was detected by thin layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid. Yield: 38%.

[0140] The structural confirmation data are as follows:

[0141] FT-IR(cm -1 ):2963(m),2920(m),1696(ν(C=N),m),1660(ν(C=N),m),1593(m),1464(s),1438(m),1390(m),1374(m ),1259(s),1209(m),1192(m),1157(m),1090(s),1061(s),1018(s),872(m),796(s),756(s),675(w).

[0142] 1 H NMR (400 MHz, CDCl 3 ), δ(ppm):6.94-6.73(m,6H,Ar-H),2.19-2.08(m,7H,CH atcampphyl,2×Ar ortho -CH 3 ),1.90-1.83(m,9H,2×Ar ortho -CH 3 ,3 / 2CH 2 at camphyl),1.46-1.41(m,1H,1 / 2CH 2 at camphyl),1.29(s,3H,CH 3 at camphyl),1.10(s,3H,CH 3 atcamphyl), 0.96(s,3H,CH 3at camphyl).

[0143] 13 C NMR (100 MHz, CDCl 3 ), δ(ppm):171.3(C=N),169.1(C=N),149.7(CN),148.5(CN),127.9,127.5,127.4,125.4,124.4,1 23.6,123.1,122.1,55.6,51.5,45.8,32.8,23.5,21.8,18.7,18.6,18.4,18.3,18.2,18.0,11.3.

[0144] Elemental analysis: C 26 H 32 N 2 (372.56) Theoretical value: C, 83.82; H, 8.66; N, 7.52. Exp. value: C, 83.79; H, 8.95; N, 7.43.

[0145] Example 2

[0146] Preparation of (1R, 3E, 4R)-N 2 , N 3 Bis(2,4-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide [L2], wherein R 1 is hydrogen, R 2 It is methyl.

[0147] Under nitrogen atmosphere, 2,4-dimethylaniline (0.73 g, 6 mmol) dissolved in toluene (20 mL) was injected into a Schlenk flask, trimethylaluminum (3 mL, 2.0 mol / L dissolved in n-hexane) was slowly added to the reaction solution with a syringe at room temperature, and then the reaction mixture was heated to reflux for 4 h. After the solution was cooled to room temperature, (D,L)-camphorquinone (0.42 g, 2.5 mmol) was added to the reaction solution, and the reflux reaction was continued for 10 h. After the reaction solution was cooled to 0 ° C, 5% NaOH aqueous solution was added dropwise to slowly hydrolyze the remaining AlMe 3 . Afterwards, the reaction solution was extracted with ethyl acetate, and the crude product was obtained after the solvent was dried by spin drying. The crude product was further purified by basic alumina column chromatography (40 / 1, petroleum ether / ethyl acetate). The eluted fraction was detected by thin layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid. Yield: 33%.

[0148] The structural confirmation data are as follows:

[0149] FT-IR(cm -1):2957(m),2920(m),2873(m),1690(ν(C=N),m),1654(ν(C=N),m),1609(m),1491(s),1447(m),1390(m),1374(m),1322(w),1287(w),1261(w),1243(w),1217(m),1197(m),1114(m),1062(m),1019(s),872(m),815(s),748(m),722(w).

[0150] 1 H NMR(400MHz,CDCl 3 ),δ(ppm):[major:minor=5:2]major isomer 7.02-6.80(m,4H,Ar-H),6.53(d,J=8.0Hz,1H,Ar-H),6.35(d,J=8.0Hz,1H,Ar-H),2.63(d,J=4.0Hz,1H,CH at camphyl),2.24(s,3H,Ar ortho -CH 3 ),2.21(s,3H,Ar ortho -CH 3 ),2.06(s,3H,Ar para -CH 3 ),2.05-1.90(m,3H,3 / 2CH 2 at camphyl),1.76(s,3H,Ar para -CH 3 ),1.56-1.50(m,1H,1 / 2CH 2 at camphyl),1.22(s,3H,CH 3 at camphyl),0.97(s,3H,CH 3 at camphyl),0.96(s,3H,CH 3 at camphyl);minor isomer 7.02-6.80(m,4H,Ar-H),6.57(d,J=8.0Hz,2H,Ar-H),2.52(d,J=4.0Hz,1H,CH at camphyl),2.32(s,3H,Ar ortho -CH 3 ),2.30(s,3H,Ar ortho -CH 3 ),2.19(s,3H,Ar para -CH 3),2.15(s,3H,Ar para -CH 3 ),1.80-1.74(m,3H,2×CH 2 atcampphyl),1.67-1.61(m,1H,1 / 2CH 2 at camphyl),1.01(s,3H,CH 3 at camphyl),0.82(s,3H,CH 3 at camphyl),0.60(s,3H,CH 3 at camphyl).

[0151] 13 C NMR (100 MHz, CDCl 3 ),δ(ppm):major isomer 171.4(C=N),167.6(C=N),148.5(CN),146.4(CN),133.8,131.5,131.1,131.0,130.4,130.1,1 26.7,126.3,125.4,118.7,117.8,116.9,55.0,50.5,45.5,32.7,24.5,20.7,17.9,11.4; minor isomer 173.1(C=N),171.4(C=N),147.8(CN),146.7(CN),133.3,132.4,131.1,130.6,128. 5,126.7,126.1,117.8,56.2,53.6,50.2,46.3,33.3,21.2,18.3,18.0,17.3,11.4.

[0152] Elemental analysis: C 26 H 32 N 2 (372.56) Theoretical value: C, 83.82; H, 8.66; N, 7.52. Exp. value: C, 83.62; H, 8.86; N, 7.38.

[0153] Example 3

[0154] Preparation of (1R, 3E, 4R)-N 2 , N 3 Bis(trimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide [L3], wherein R 1 is methyl, R 2 It is methyl.

[0155] Under nitrogen atmosphere, 2,4,6-trimethylaniline (0.81 g, 6 mmol) dissolved in toluene (20 mL) was injected into a Schlenk flask, trimethylaluminum (3 mL, 2.0 mol / L dissolved in n-hexane) was slowly added to the reaction solution with a syringe at room temperature, and then the reaction mixture was heated to reflux for 4 h. After the solution was cooled to room temperature, (D,L)-camphorquinone (0.42 g, 2.5 mmol) was added to the reaction solution, and the reflux reaction was continued for 10 h. After the reaction solution was cooled to 0 ° C, 5% NaOH aqueous solution was added dropwise to slowly hydrolyze the remaining AlMe 3 . Afterwards, the reaction solution was extracted with ethyl acetate, and the crude product was obtained after the solvent was dried by spin drying. The crude product was further purified by basic alumina column chromatography (40 / 1, petroleum ether / ethyl acetate). The eluted fraction was detected by thin layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid. Yield: 32%.

[0156] The structural confirmation data are as follows:

[0157] FT-IR(cm -1 ):2959(m),2912(m),1693(ν(C=N),m),1660(ν(C=N),m),1475(s),1390(m),1372(m ),1213(s),1167(m),1142(m),1110(m),1062(m),1017(m),852(s),770(m),689(m).

[0158] 1 H NMR (400 MHz, CDCl 3 ),δ(ppm):6.74(s,2H,Ar-H),6.68(s,2H,Ar-H),2.29-2.03(m,14H,CH at camphyl,1 / 2CH 2 at camphyl,4×Ar ortho -CH 3 ),1.93-1.76(m,8H,CH 2 atcamphyl,2×Ar para -CH 3 ),1.44-1.39(m,1H,1 / 2CH 2 at camphyl),1.27(s,3H,CH 3 atcamphyl), 1.08(s,3H,CH 3 at camphyl),0.95(s,3H,CH 3 at camphyl).

[0159] 13 C NMR (100 MHz, CDCl 3 ), δ(ppm):171.4(C=N),169.2(C=N),147.2(CN),146.1(CN),132.3,130.9,128.6,128.5,128.2,1 25.3,124.2,124.1,123.3,55.6,51.5,45.7,32.9,23.5,21.7,20.9,20.7,18.5,18.3,18.1,11.4.

[0160] Elemental analysis: C 28 H 36 N 2 (400.61) Theoretical value: C, 83.95; H, 9.06; N, 6.99. Exp. value: C, 83.66; H, 9.35; N, 6.83.

[0161] Example 4

[0162] Preparation of (1R, 3E, 4R)-N 2 , N 3 -bis(4-(bis(4-fluorophenyl)methyl)-2,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide [L4], wherein R 1 is methyl, R 2 It is bis(4-fluorophenyl)methyl.

[0163] Under nitrogen atmosphere, 4-(bis(4-fluorophenyl)methyl)-2,6-dimethylaniline (1.94 g, 6 mmol) dissolved in toluene (20 mL) was injected into a Schlenk flask, and trimethylaluminum (3 mL, 2.0 mol / L dissolved in n-hexane) was slowly added to the reaction solution with a syringe at room temperature, and then the reaction mixture was heated to reflux for 4 h. After the solution was cooled to room temperature, (D,L)-camphorquinone (0.42 g, 2.5 mmol) was added to the reaction solution, and the reflux reaction was continued for 10 h. After the reaction solution was cooled to 0 ° C, 5% NaOH aqueous solution was added dropwise to slowly hydrolyze the remaining AlMe 3 . Afterwards, the reaction solution was extracted with ethyl acetate, and the crude product was obtained after the solvent was dried by spin drying. The crude product was further purified by basic alumina column chromatography (40 / 1, petroleum ether / ethyl acetate). The eluted fraction was detected by thin layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid. Yield: 21%.

[0164] The structural confirmation data are as follows:

[0165] FT-IR(cm-1 ): 2963 (m), 2918 (m), 1688 (ν(C=N), m), 1655 (ν(C=N), m), 1601 (m), 1504 (s), 1474 (m), 1259 (m), 1220 (s), 1156 (m), 1093 (m), 1016 (m), 819 (s), 795 (s), 677 (w).

[0166] 1 H NMR (400 MHz, CDCl 3 ), δ (ppm) 7.11 - 7.08 (m, 4H, Ar-H), 7.01 - 6.87 (m, 8H, Ar-H), 6.76 - 6.71 (m, 4H, Ar-H), 6.65 (s, 2H, Ar-H), 6.55 (s, 2H, Ar-H), 5.40 (s, 1H, CH(p-FPh) 2 ), 5.37 (s, 1H, CH(p-FPh) 2 ), 2.18 (s, 1H, CH at camphyl), 2.09 - 1.73 (m, 15H, 4×Ar ortho -CH 3 , 3 / 2CH 2 at camphyl), 1.43 - 1.37 (m, 1H, 1 / 2CH 2 at camphyl), 1.28 (s, 3H, CH 3 at camphyl), 1.07 (s, 3H, CH 3 at camphyl), 0.97 (s, 3H, CH 3 at camphyl).

[0167] 13 C NMR (100 MHz, CDCl 3 ), δ (ppm): 172.1 (C=N), 169.1 (C=N), 162.8 (C-N), 162.6 (C-N), 160.4, 160.2, 148.9, 146.6, 140.6, 140.0, 138.3, 136.7, 131.0, 130.9, 130.8, 128.7, 128.4, 128.2, 125.2, 124.9, 124.2, 124.0, 115.4, 115.2, 114.9, 114.7, 55.5, 55.0, 54.5, 51.4, 45.9, 32.8, 23.6, 21.8, 18.8, 18.4, 18.3, 18.1, 11.30.

[0168] Elemental analysis: C52 H 48 F 4 N 2 (776.96) Theoretical value: C, 80.39; H, 6.23; N, 3.61. Exp. value: C, 80.06; H, 6.35; N, 3.85.

[0169] Example 5

[0170] Preparation of (1R, 3E, 4R)-N 2 , N 3 -bis(2-(bis(4-fluorophenyl)methyl)-4,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide [L5], wherein R 1 is bis(4-fluorophenyl)methyl, R 2 It is methyl.

[0171] Under nitrogen atmosphere, 2-(bis(4-fluorophenyl)methyl)-4,6-dimethylaniline (1.94 g, 6 mmol) dissolved in toluene (20 mL) was injected into a Schlenk flask, trimethylaluminum (3 mL, 2.0 mol / L dissolved in n-hexane) was slowly added to the reaction solution with a syringe at room temperature, and then the reaction mixture was heated to reflux for 4 h. After the solution was cooled to room temperature, (D,L)-camphorquinone (0.42 g, 2.5 mmol) was added to the reaction solution, and the reflux reaction was continued for 10 h. After the reaction solution was cooled to 0 ° C, 5% NaOH aqueous solution was added dropwise to slowly hydrolyze the remaining AlMe 3 . Afterwards, the reaction solution was extracted with ethyl acetate, and the crude product was obtained after the solvent was dried by spin drying. The crude product was further purified by basic alumina column chromatography (40 / 1, petroleum ether / ethyl acetate). The eluted fraction was detected by a thin layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid. Yield: 16%.

[0172] The structural confirmation data are as follows:

[0173] FT-IR(cm -1 ):2958(m),2908(m),1686(ν(C=N),m),1651(ν(C=N),m),1602(m),1505(s),1448(m),1298( w),1224(s),1157(m),1098(m),1058(m),1018(m),839(s),794(m),767(m),731(w),680(w).

[0174] 1 H NMR (400 MHz, CDCl 3), δ (ppm): 7.06 - 6.78 (m, 16H, Ar - H), 6.66 (t, J = 8 Hz, 2H, Ar - H), 6.57 (s, 1H, Ar - H), 6.41 (s, 1H, Ar - H), 5.38 (s, 1H, CH(p - FPh) 2 ), 5.17 (s, 1H, CH(p - FPh) 2 ), 2.25 - 2.08 (m, 8H, 2×Ar ortho -CH 3 , CH at camphyl, 1 / 2CH 2 at camphyl), 2.00 (s, 3H, Ar para -CH 3 ), 1.89 (s, 3H, Ar para -CH 3 ), 1.64 - 1.55 (m, 1H, 1 / 2CH 2 at camphyl), 1.36 - 1.31 (m, 2H, CH 2 at camphyl), 1.08 (s, 3H, CH 3 at camphyl), 0.92 (s, 3H, CH 3 at camphyl), 0.85 (s, 3H, CH 3 at camphyl).

[0175] 13 C NMR (100 MHz, CDCl 3 ), δ (ppm): 171.3 (C=N), 171.0 (C=N), 162.8 (C - N), 160.4 (C - N), 144.3, 142.0, 139.8, 139.0, 138.7, 133.0, 132.1, 131.3, 131.2, 131.1, 130.9, 130.8, 130.7, 130.6, 130.0, 129.6, 129.1, 127.7, 124.3, 123.7, 115.2, 115.1, 115.0, 114.9, 114.8, 114.7, 55.9, 51.5, 50.6, 48.3, 45.7, 32.6, 23.6, 22.9, 21.1, 21.0, 19.7, 19.4, 18.0, 10.8.

[0176] Elemental analysis: C 52 H 48 F 4 N 2(776.96) Theoretical value: C, 80.39; H, 6.23; N, 3.61. Exp. value: C, 80.12; H, 6.56; N, 3.74.

[0177] Example 6

[0178] Preparation of 1R, 3E, 4R)-N 2 , N 3 -bis(2,4-bis(4-fluorophenyl)methyl)-6-methylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide [L6], wherein R 1 is bis(4-fluorophenyl)methyl, R 2 It is bis(4-fluorophenyl)methyl.

[0179] Under nitrogen atmosphere, 2,4-bis(4-fluorophenyl)methyl)-6-methylaniline (3.07 g, 6 mmol) dissolved in toluene (20 mL) was injected into a Schlenk flask, and trimethylaluminum (3 mL, 2.0 mol / L dissolved in n-hexane) was slowly added to the reaction solution with a syringe at room temperature, and then the reaction mixture was heated to reflux for 4 h. After the solution was cooled to room temperature, (D,L)-camphorquinone (0.42 g, 2.5 mmol) was added to the reaction solution, and the reflux reaction was continued for 10 h. After the reaction solution was cooled to 0 ° C, 5% NaOH aqueous solution was added dropwise to slowly hydrolyze the remaining AlMe 3 . Afterwards, the reaction solution was extracted with ethyl acetate, and the crude product was obtained after the solvent was dried by spin drying. The crude product was further purified by basic alumina column chromatography (40 / 1, petroleum ether / ethyl acetate). The eluted fraction was detected by thin layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain an orange-yellow solid. Yield: 11%.

[0180] The structural confirmation data are as follows:

[0181] FT-IR(cm -1 ):2963(m),2915(m),1685(ν(C=N),m),1652(ν(C=N),m),1600(m),1504(s),1469(m ),1411(w),1222(s),1156(m),1094(m),1058(m),1016(m),825(s),792(m),661(w).

[0182] 1 H NMR (400 MHz, CDCl 3),δ(ppm):[major:minor=3:1]major isomer 6.97-6.70(m,34H,Ar-H),6.58-6.37(m,6H,Ar-H),6.18(s,1H,Ar-H),5.25(s,2H,CH(p-FPh) 2 ),5.17(s,2H,CH(p-FPh) 2 ),2.24(d,J=4Hz,1H,CH at camphyl),2.08(s,3H,Ar ortho -CH 3 ),1.85(s,3H,Ar ortho -CH 3 ),1.64-1.58(m,4H,2×CH 2 at camphyl),1.02(s,3H,CH 3 at camphyl),0.88(s,3H,CH 3 at camphyl),0.85(s,3H,CH 3 at camphyl);minor isomer 6.97-6.70(m,34H,Ar-H),6.58-6.37(m,6H,Ar-H),6.24(s,1H,Ar-H),5.34-5.32(m,4H,CH(p-FPh) 2 ),2.19(d,J=4Hz,1H,CH at camphyl),2.03(s,3H,Ar ortho -CH 3 ),1.83(s,3H,Ar ortho -CH 3 ),1.84-1.78(m,2H,CH 2 at camphyl),1.36-1.26(m,2H,CH 2 at camphyl),0.87(s,3H,CH 3 atcamphyl),0.79(s,3H,CH 3 at camphyl),0.64(s,3H,CH 3 at camphyl).

[0183] 13 C NMR(100MHz,CDCl 3),δ(ppm):major isomer 162.8(C=N),160.3(C=N),140.2(CN),138.9(CN),138.6,131.1,131.0,130.9,130.8,130.7,130.6,130.5,130.4,124.8,124.1,115 minor isomer 171.0(C=N),162.7(C=N),145.4(CN),141.5(CN),139.6,131.1,131.0,130.9,130.8,130.7,130.6,130.5,130.4,126.1,125.5,115.4,1 15.3,115.2,115.1,115.0,114.9,114.8,114.7,55.9,54.7,51.8,50 .9,48.6,45.8,34.4,31.4,23.5,23.1,22.6,19.8,19.2,18.0,10.9.

[0184] Elemental analysis: C 76 H 60 F 8 N 2 (1153.32) Theoretical value: C, 79.15; H, 5.24; N, 2.43. Exp. value: C, 79.08; H, 5.61; N, 2.55.

[0185] Example 7

[0186] Preparation of [(1R, 3E, 4R)-N 2 , N 3 bis(2,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide]nickel(II) bromide [complex C1], wherein R 1 is methyl, R 2 is hydrogen, and X is bromine.

[0187] Under nitrogen protection, the (1R, 3E, 4R)-N prepared in Example 1 was added to 2 , N 3To a solution of bis(2,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide (0.075 g, 0.20 mmol) in dichloromethane (20 mL) was added an equivalent of (DME)NiBr 2 (0.063 g, 0.20 mmol). After the mixed solution was stirred at room temperature for 12 hours, most of the dichloromethane was removed under reduced pressure and the solution was concentrated to about 3 ml. Hexane (20 mL) was added thereto to recrystallize the product and form a precipitate. The collected solid was washed with 3×10 mL of hexane and dried under vacuum to obtain a yellow solid. Yield: 76%.

[0188] The structural confirmation data are as follows:

[0189] FT-IR(cm -1 ):2957(m),2915(m),1677(ν(C=N),m),1633(ν(C=N),m),1610(m),1451(s),1390(m),1378(m),12 44(m),1218(s),1175(m),1149(m),1108(m),1070(m),1039(m),856(s),789(w),764(w),714(m).

[0190] Elemental analysis: C 26 H 32 Br 2 N 2 Ni (591.06) theoretical value: C, 52.84; H, 5.46; N, 4.74. Exp. value: C, 52.66; H, 5.71; N, 4.55.

[0191] Example 8

[0192] Preparation of [(1R, 3E, 4R)-N 2 , N 3 bis(2,4-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimino]nickel(II) bromide [complex C2], wherein R 1 is hydrogen, R 2 is methyl, and X is bromine.

[0193] Under nitrogen protection, the (1R, 3E, 4R)-N prepared in Example 1 was added to 2 , N 3 To a solution of bis(2,4-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide (0.075 g, 0.20 mmol) in dichloromethane (20 mL) was added an equivalent of (DME)NiBr2 (0.063 g, 0.20 mmol). After the mixed solution was stirred at room temperature for 12 hours, most of the dichloromethane was removed under reduced pressure and the solution was concentrated to about 3 ml. Hexane (20 mL) was added thereto to recrystallize the product and form a precipitate. The collected solid was washed with 3×10 mL of hexane and dried under vacuum to obtain a yellow solid. Yield: 82%.

[0194] The structural confirmation data are as follows:

[0195] FT-IR(cm -1 ):2952(m),2914(m),1675(ν(C=N),m),1639(ν(C=N),m),1610(m),1453(s),1395(m),1378(m),12 40(m),1216(s),1170(m),1148(m),1106(m),1070(m),1030(m),853(s),789(w),762(w),710(m).

[0196] Elemental analysis: C 26 H 32 Br 2 N 2 Ni (591.06) theoretical value: C, 52.84; H, 5.46; N, 4.74. Exp. value: C, 52.70; H, 5.66; N, 4.62.

[0197] Example 9

[0198] Preparation of [(1R, 3E, 4R)-N 2 , N 3 bis(trimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide]nickel(II) bromide [complex C3], wherein R 1 is methyl, R 2 is methyl, and X is bromine.

[0199] Under nitrogen protection, the (1R, 3E, 4R)-N prepared in Example 1 was added to 2 , N 3 To a solution of bis(trimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide (0.080 g, 0.20 mmol) in dichloromethane (20 mL) was added an equivalent of (DME)NiBr 2(0.063 g, 0.20 mmol). After the mixed solution was stirred at room temperature for 12 hours, most of the dichloromethane was removed under reduced pressure and the solution was concentrated to about 3 ml. Hexane (20 mL) was added thereto to recrystallize the product and form a precipitate. The collected solid was washed with 3×10 mL of hexane and dried under vacuum to obtain a yellow solid. Yield: 81%.

[0200] The structural confirmation data are as follows:

[0201] FT-IR(cm -1 ):2958(m),2917(m),1676(ν(C=N),m),1638(ν(C=N),m),1612(m),1450(s),1397(m),1379(m),12 44(m),1215(s),1172(m),1149(m),1107(m),1071(m),1034(m),854(s),788(w),761(w),711(m).

[0202] Elemental analysis: C 28 H 36 Br 2 N 2 Ni (619.11) theoretical value: C, 54.32; H, 5.86; N, 4.52. Exp. value: C, 54.62; H, 5.89; N, 4.67.

[0203] Example 10

[0204] Preparation of [(1R, 3E, 4R)-N 2 , N 3 -bis(4-(bis(4-fluorophenyl)methyl)-2,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimino]nickel(II) bromide [complex C4], wherein R 1 is methyl, R 2 is bis(4-fluorophenyl)methyl, and X is bromine.

[0205] Under nitrogen protection, the (1R, 3E, 4R)-N prepared in Example 1 was added to 2 , N 3 To a solution of bis(4-(bis(4-fluorophenyl)methyl)-2,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide (0.16 g, 0.20 mmol) in dichloromethane (20 mL) was added an equivalent of (DME)NiBr 2(0.063 g, 0.20 mmol). After the mixed solution was stirred at room temperature for 12 hours, most of the dichloromethane was removed under reduced pressure and the solution was concentrated to about 3 ml. Hexane (20 mL) was added thereto to recrystallize the product and form a precipitate. The collected solid was washed with 3×10 mL of hexane and dried under vacuum to obtain a yellow solid.

[0206] Yield: 85%.

[0207] The structural confirmation data are as follows:

[0208] FT-IR(cm -1 ):2965(m),2918(m),1674(ν(C=N),m),1633(ν(C=N),m),1603(m),1505(s) ,1450(m),1262(w),1220(s),1158(m),1096(m),1015(m),836(s),793(w).

[0209] Elemental analysis: C 52 H 48 Br 2 F 4 N 2 Ni (995.47) theoretical value: C, 62.74; H, 4.86; N, 2.81. Exp. value: C, 62.58; H, 4.97; N, 2.85.

[0210] Embodiment 11

[0211] Preparation of [(1R, 3E, 4R)-N 2 , N 3 -bis(2-(bis(4-fluorophenyl)methyl)-4,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide]nickel(II) bromide [complex C5], wherein R 1 is methyl, R 2 is bis(4-fluorophenyl)methyl, and X is bromine.

[0212] Under nitrogen protection, the (1R, 3E, 4R)-N prepared in Example 1 was added to 2 , N 3 To a solution of bis(2-(bis(4-fluorophenyl)methyl)-4,6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide (0.16 g, 0.20 mmol) in dichloromethane (20 mL) was added an equivalent of (DME)NiBr 2(0.063 g, 0.20 mmol). After the mixed solution was stirred at room temperature for 12 hours, most of the dichloromethane was removed under reduced pressure and the solution was concentrated to about 3 ml. Hexane (20 mL) was added thereto to recrystallize the product and form a precipitate. The collected solid was washed with 3×10 mL of hexane and dried under vacuum to obtain a yellow solid.

[0213] Yield: 77%.

[0214] The structural confirmation data are as follows:

[0215] FT-IR(cm -1 ):2966(m),2925(m),1663(ν(C=N),m),1626(ν(C=N),m),1603(m),1506(s),1454(m ),1299(w),1225(s),1158(m),1098(m),1038(m),1018(m),832(m),723(w),686(w).

[0216] Elemental analysis: C 52 H 48 Br 2 F 4 N 2 Ni (995.47) theoretical value: C, 62.74; H, 4.86; N, 2.81. Exp. value: C, 62.39; H, 5.12; N, 2.91.

[0217] Example 12

[0218] Preparation of [(1R, 3E, 4R)-N 2 , N 3 -bis(2,4-(bis(4-fluorophenyl)methyl)-6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimino]nickel(II) bromide [complex C6], wherein R 1 is methyl, R 2 is bis(4-fluorophenyl)methyl, and X is bromine.

[0219] Under nitrogen protection, the (1R, 3E, 4R)-N prepared in Example 1 was added to 2 , N 3 To a solution of bis(2,4-(bis(4-fluorophenyl)methyl)-6-dimethylphenyl)-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diimide (0.23 g, 0.20 mmol) in dichloromethane (20 mL) was added an equivalent of (DME)NiBr 2(0.063 g, 0.20 mmol). After the mixed solution was stirred at room temperature for 12 hours, most of the dichloromethane was removed under reduced pressure and the solution was concentrated to about 3 ml. Hexane (20 mL) was added thereto to recrystallize the product and form a precipitate. The collected solid was washed with 3×10 mL of hexane and dried under vacuum to obtain a yellow solid.

[0220] Yield: 81%.

[0221] The structural confirmation data are as follows:

[0222] FT-IR(cm -1 ):2966(m),2916(m),1669(ν(C=N),m),1651(ν(C=N),w),1601(m),1504(s),14 49(m),1411(w),1221(s),1157(m),1097(m),1015(m),831(s),793(m),724(w).

[0223] Elemental analysis: C 76 H 60 Br 2 F 8 N 2 Ni (1371.82) theoretical value: C, 66.54; H, 4.41; N, 2.04. Exp. value: C, 66.28; H, 4.56; N, 2.25.

[0224] Embodiment 13

[0225] Ethylene polymerization under pressure using complex C5 and MAO as co-catalyst:

[0226] Under ethylene atmosphere, 25mL toluene, 25mL toluene solution of catalyst C1 (2μmol), 2.7mL co-catalyst MAO (1.46mol / L toluene solution), and 50mL toluene were added to a 250mL stainless steel autoclave in sequence, at which Al / Ni = 2000:1. Mechanical stirring began, maintained at 400 rpm, and when the polymerization temperature reached 30°C, ethylene was filled into the reactor, and the polymerization reaction began. The ethylene pressure was maintained at 10atm at 30°C and stirred for 30min. The reaction solution was neutralized with 5% hydrochloric acid-acidified ethanol solution to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0227] Polymerization activity: 5.7×10 6 g·mol -1 (Ni)·h -1 , polymer T m =117.7℃. (T mis the melting temperature of the polymer, obtained by DSC test), the polymer molecular weight M w =14.9×10 5 g·mol -1 , PDI=2.0(M w is the mass average molecular weight of the polymer, obtained by temperature-raising GPC test).

[0228] Embodiment 14

[0229] Ethylene polymerization under pressure using complex C5 and MMAO co-catalyst:

[0230] Under ethylene atmosphere, 25mL toluene, 25mL toluene solution of catalyst C1 (2μmol), 2.1mL co-catalyst MMAO (1.93mol / L heptane solution), and 50mL toluene were added to a 250mL stainless steel autoclave in sequence, at which Al / Ni = 2000:1. Mechanical stirring began, maintained at 400 rpm, and when the polymerization temperature reached 30°C, ethylene was charged into the reactor, and the polymerization reaction began. The ethylene pressure was maintained at 10atm at 30°C and stirred for 30min. The reaction solution was neutralized with 5% hydrochloric acid-acidified ethanol solution to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0231] Polymerization activity: 6.0×10 6 g·mol -1 (Ni)·h -1 , polymer T m =118.7℃. (T m is the melting temperature of the polymer, obtained by DSC test), the polymer molecular weight M w =14.0×10 5 g·mol -1 , PDI=1.5(M w is the mass average molecular weight of the polymer, obtained by temperature-raising GPC test).

[0232] Embodiment 15

[0233] Using complex C5 and Me 2 Ethylene polymerization under pressure with AlCl cocatalyst:

[0234] Under ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C1 (2 μmol), 1.0 mL of a co-catalyst Me 2AlCl (1.00 mol / L toluene solution) and 50 mL toluene were added to a 250 mL stainless steel autoclave in sequence, at which point Al / Ni = 500:1. Mechanical stirring was started and maintained at 400 rpm. When the polymerization temperature reached 30°C, ethylene was charged into the reactor and the polymerization reaction began. The ethylene pressure was maintained at 10 atm at 30°C and stirred for 30 minutes. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0235] Polymerization activity: 6.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =117.0℃. (T m is the melting temperature of the polymer, obtained by DSC test), the polymer molecular weight M w =23.7×10 5 g·mol -1 , PDI = 1.6 (M w is the mass average molecular weight of the polymer, obtained by temperature-raising GPC test).

[0236] Example 16

[0237] Ethylene polymerization under pressure using complex C5 and MMAO co-catalyst:

[0238] a) Under ethylene atmosphere, 25 mL of toluene, 25 mL of toluene solution of catalyst C1 (2 μmol), 2.1 mL of co-catalyst MMAO (1.93 mol / L heptane solution), and 50 mL of toluene are added to a 250 mL stainless steel autoclave in sequence, at which Al / Ni = 2000:1. Mechanical stirring begins, maintained at 400 rpm, and when the polymerization temperature reaches 40°C, ethylene is charged into the reactor to start the polymerization reaction. The ethylene pressure is maintained at 10 atm at 30°C and stirred for 30 min. The reaction solution is neutralized with ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which is washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0239] Polymerization activity: 6.34×10 6 g·mol -1 (Ni)·h -1 , polymer T m =117.5℃. (T m is the melting temperature of the polymer, obtained by DSC test), the polymer molecular weight M w =13.7×10 5 g·mol -1 , PDI = 2.5 (M wis the mass average molecular weight of the polymer, obtained by temperature-raising GPC test).

[0240] b) is basically the same as a), except that the polymerization temperature is 50°C. Polymerization activity: 6.7×10 6 g·mol -1 (Ni)·h -1 , polymer T m =116.1℃,M w =13.4×10 5 g·mol -1 , PDI=2.2.

[0241] c) is basically the same as a), except that the polymerization temperature is 60°C. Polymerization activity: 7.2×10 6 g·mol -1 (Ni)·h -1 , polymer T m =115.6℃,M w =11.6×10 5 g·mol -1 , PDI=1.6.

[0242] d) is basically the same as a), except that the polymerization temperature is 70°C. Polymerization activity: 9.0×10 6 g·mol -1 (Ni)·h -1 , polymer T m =108.4℃,M w =11.6×10 5 g·mol -1 , PDI=1.7.

[0243] e) is basically the same as a), except that the polymerization temperature is 80°C. Polymerization activity: 7.6×10 6 g·mol -1 (Ni)·h -1 , polymer T m =107.2℃,M w =10.0×10 5 g·mol -1 , PDI=2.1.

[0244] f) is basically the same as a), except that the polymerization temperature is 90°C. Polymerization activity: 4.7×10 6 g·mol -1 (Ni)·h -1 , polymer T m =102.4℃,M w =9.6×10 5 g·mol -1, PDI=1.8.

[0245] g) is basically the same as d), except that the amount of the co-catalyst is 1.0 mL of co-catalyst MMAO (1.93 mol / L heptane solution), and Al / Ni=1000:1. Polymerization activity: 7.4×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.8℃,M w =11.5×10 5 g·mol -1 , PDI=1.8.

[0246] h) is basically the same as d), except that the amount of the co-catalyst used is 1.6 mL of co-catalyst MMAO (1.93 mol / L heptane solution), and Al / Ni=1500:1. Polymerization activity: 9.4×10 6 g·mol -1 (Ni)·h -1 , polymer T m =112.8℃,M w =11.8×10 5 g·mol -1 , PDI=1.9.

[0247] Take 100 mg of the obtained polymer, dissolve it in 5 mL of deuterated tetrachloroethane, and test the polymer at 100 °C. 13 The signal was accumulated 2000 times, and the peak shift was between 10-40 (ppm), indicating the shift of methyl, methylene and methine groups, proving that the obtained polymer was branched polyethylene with a medium branching degree of 33 / 1000C and a long chain branch ratio of 12.4% (for details, see Figure 3 ).

[0248] i) is basically the same as d), except that the amount of the co-catalyst used is 2.6 mL of the co-catalyst MMAO (1.93 mol / L heptane solution), and the Al / Ni ratio is 2500:1. Polymerization activity: 8.0×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.6℃,M w =10.3×10 5 g·mol -1 , PDI=1.8.

[0249] j) is basically the same as d), except that the amount of the co-catalyst used is 3.1 mL of the co-catalyst MMAO (1.93 mol / L heptane solution), and the Al / Ni ratio is 3000:1. Polymerization activity: 7.7×10 6 g·mol -1 (Ni)·h -1 , polymer T m =107.9℃,M w =10.2×10 5 g·mol -1 , PDI=1.5.

[0250] k) is basically the same as h), except that the polymerization time is 5 min. Polymerization activity: 16.1×10 6 g·mol -1 (Ni)·h -1 , polymer T m =110.0℃,M w =9.3×10 5 g·mol -1 , PDI=1.8.

[0251] l) is basically the same as h), except that the polymerization time is 15 min. Polymerization activity: 11.6×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.5℃,M w =10.4×10 5 g·mol -1 , PDI=1.9.

[0252] m) is basically the same as h), except that the polymerization time is 45 min. Polymerization activity: 8.1×10 6 g·mol -1 (Ni)·h -1 , polymer T m =108.2℃,M w =12.7×10 5 g·mol -1 , PDI=1.9.

[0253] n) is basically the same as h), except that the polymerization time is 60 min. Polymerization activity: 7.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =118.2℃,M w =15.4×10 5 g·mol -1, PDI=2.3.

[0254] Embodiment 17

[0255] Ethylene polymerization under pressure using complex C1 and MMAO co-catalyst:

[0256] Basically the same as Example 16h), except that the main catalyst is C1. Polymerization activity: 1.8×10 6 g·mol -1 (Ni)·h -1 , polymer T m =83.6℃,M w =0.8×10 5 g·mol -1 , PDI=2.0.

[0257] Embodiment 18

[0258] Ethylene polymerization under pressure using complex C2 and MMAO co-catalyst:

[0259] Basically the same as Example 16h), except that the main catalyst is C2. Polymerization activity: 1.8×10 6 g·mol -1 (Ni)·h -1 , polymer T m =81.2℃,M w =0.02×10 5 g·mol -1 , PDI=2.2.

[0260] Embodiment 19

[0261] Ethylene polymerization under pressure using complex C3 and MMAO co-catalyst:

[0262] Basically the same as Example 16h), except that the main catalyst is C3. Polymerization activity: 2.0×10 6 g·mol -1 (Ni)·h -1 , polymer T m =84.8℃,M w =0.8×10 5 g·mol -1 , PDI=1.7.

[0263] Embodiment 20

[0264] Ethylene polymerization under pressure using complex C4 and MMAO co-catalyst:

[0265] Basically the same as Example 16h), except that the main catalyst is C4. Polymerization activity: 1.5×106 g·mol -1 (Ni)·h -1 , polymer T m =92.2℃,M w =0.6×10 5 g·mol -1 , PDI=1.9.

[0266] Embodiment 21

[0267] Ethylene polymerization under pressure using complex C6 and MMAO as a co-catalyst:

[0268] Basically the same as Example 16h), except that the main catalyst is C6. Polymerization activity: 7.6×10 6 g·mol -1 (Ni)·h -1 , polymer T m =116.3℃,M w =16.3×10 5 g·mol -1 , PDI=1.6.

[0269] Embodiment 22

[0270] Using complex C5 and Me 2 Ethylene polymerization under pressure with AlCl cocatalyst:

[0271] a) In an ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C5 (2 μmol), 1.0 mL of a co-catalyst Me 2 AlCl (1.00 mol / L toluene solution) and 50 mL toluene were added to a 250 mL stainless steel autoclave. At this time, Al / Ni = 500:1. Mechanical stirring was started and maintained at 400 rpm. When the polymerization temperature reached 40°C, ethylene was charged into the reactor and the polymerization reaction began. The ethylene pressure was maintained at 10 atm at 30°C and stirred for 30 minutes. The reaction solution was neutralized with 5% hydrochloric acid-acidified ethanol solution to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0272] Polymerization activity: 7.0×10 6 g·mol -1 (Ni)·h -1 , polymer T m =113.7℃. (T m is the melting temperature of the polymer, obtained by DSC test), the polymer molecular weight M w =17.7×10 5 g·mol -1 , PDI = 1.9 (Mw is the mass average molecular weight of the polymer, obtained by temperature-raising GPC test).

[0273] b) is basically the same as a), except that the polymerization temperature is 50°C. Polymerization activity: 7.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =111.7℃,M w =17.0×10 5 g·mol -1 , PDI=2.2.

[0274] c) is basically the same as a), except that the polymerization temperature is 60°C. Polymerization activity: 8.0×10 6 g·mol -1 (Ni)·h -1 , polymer T m =110.9℃,M w =9.9×10 5 g·mol -1 , PDI=1.9.

[0275] d) is basically the same as a), except that the polymerization temperature is 70°C. Polymerization activity: 8.8×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.4℃,M w =9.6×10 5 g·mol -1 , PDI=1.8.

[0276] e) is basically the same as a), except that the polymerization temperature is 80°C. Polymerization activity: 9.2×10 6 g·mol -1 (Ni)·h -1 , polymer T m =104.9℃,M w =8.9×10 5 g·mol -1 , PDI=2.0.

[0277] f) is basically the same as a), except that the polymerization temperature is 90°C. Polymerization activity: 4.6×10 6 g·mol -1 (Ni)·h -1 , polymer T m =101.8℃,M w =6.6×10 5 g·mol-1 , PDI=1.8.

[0278] g) is basically the same as e), except that the amount of the co-catalyst used is 0.4 mL of the co-catalyst Me 2 AlCl (1.00 mol / L toluene solution), Al / Ni = 200:1. Polymerization activity: 9.1×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.3℃,M w =11.7×10 5 g·mol -1 , PDI=1.9.

[0279] h) is basically the same as e), except that the amount of the co-catalyst used is 0.6 mL of the co-catalyst Me 2 AlCl (1.00 mol / L toluene solution), Al / Ni = 300:1. Polymerization activity: 9.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =104.6℃,M w =11.1×10 5 g·mol -1 , PDI=2.3.

[0280] i) is basically the same as e), except that the amount of the co-catalyst used is 0.8 mL of the co-catalyst Me 2 AlCl (1.00 mol / L toluene solution), Al / Ni = 400:1. Polymerization activity: 11.2×10 6 g·mol -1 (Ni)·h -1 , polymer T m =105.5℃,M w =9.5×10 5 g·mol -1 , PDI=2.1.

[0281] Take 100 mg of the obtained polymer, dissolve it in 5 mL of deuterated tetrachloroethane, and test the polymer at 100 °C. 13 The signal was accumulated 2000 times, and the signal peak shift was between 10-40 (ppm), indicating the shift of methyl, methylene and methine groups, proving that the obtained polymer was branched polyethylene with a medium branching degree of 30 / 1000C and a long chain branch ratio of 9.3% (for details, see Figure 4 ).

[0282] j) is basically the same as e), except that the amount of the co-catalyst used is 1.2 mL of the co-catalyst Me 2 AlCl (1.00 mol / L toluene solution), Al / Ni = 600:1. Polymerization activity: 7.9×10 6 g·mol -1 (Ni)·h -1 , polymer T m =105.3℃,M w =8.2×10 5 g·mol -1 , PDI=1.8.

[0283] k) is basically the same as i), except that the polymerization time is 5 min. Polymerization activity: 21.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =113.9℃,M w =7.6×10 5 g·mol -1 , PDI=2.6.

[0284] l) is basically the same as i), except that the polymerization time is 15 min. Polymerization activity: 14.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.2℃,M w =7.9×10 5 g·mol -1 , PDI=2.8.

[0285] m) is basically the same as i), except that the polymerization time is 45 min. Polymerization activity: 9.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =106.0℃,M w =13.5×10 5 g·mol -1 , PDI=2.4.

[0286] n) is basically the same as i), except that the polymerization time is 60 min. Polymerization activity: 8.3×10 6 g·mol -1 (Ni)·h -1 , polymer T m =105.6℃,M w =15.6×10 5 g·mol-1 , PDI=3.0.

[0287] Embodiment 23

[0288] Using complex C1 and Me 2 Ethylene polymerization under pressure with AlCl cocatalyst:

[0289] Basically the same as Example 22i), except that the main catalyst is C1. Polymerization activity: 3.7×10 6 g·mol -1 (Ni)·h -1 , polymer T m =71.5℃,M w =0.5×10 5 g·mol -1 , PDI=2.0.

[0290] Embodiment 24

[0291] Using complex C2 and Me 2 Ethylene polymerization under pressure with AlCl cocatalyst:

[0292] Basically the same as Example 22i), except that the main catalyst is C2. Polymerization activity: 2.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =74.4℃,M w =0.03×10 5 g·mol -1 , PDI=2.6.

[0293] Embodiment 25

[0294] Using complex C3 and Me 2 Ethylene polymerization under pressure with AlCl cocatalyst:

[0295] Basically the same as Example 22i), except that the main catalyst is C3. Polymerization activity: 5.8×10 6 g·mol -1 (Ni)·h -1 , polymer T m =63.4℃,M w =0.5×10 5 g·mol -1 , PDI=1.9.

[0296] Embodiment 26

[0297] Using complex C4 and Me 2Ethylene polymerization under pressure with AlCl cocatalyst:

[0298] Basically the same as Example 22i), except that the main catalyst is C4. Polymerization activity: 4.5×10 6 g·mol -1 (Ni)·h -1 , polymer T m =71.9℃,M w =0.6×10 5 g·mol -1 , PDI=1.9.

[0299] Embodiment 27

[0300] Using complex C6 and Me 2 Ethylene polymerization under pressure with AlCl cocatalyst:

[0301] Basically the same as Example 22i), except that the main catalyst is C6. Polymerization activity: 7.8×10 6 g·mol -1 (Ni)·h -1 , polymer T m =109.3℃,M w =11.5×10 5 g·mol -1 , PDI=1.9.

[0302] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A compound having a structure represented by formula (II-5): Formula (II-5).

2. Nickel complex having the structure shown in formula (I-5): Formula (I-5).

3. A method for preparing the nickel complex represented by formula (I-5) in claim 2, comprising the following steps: The compound of the structure shown in formula (II-5) in claim 1 is reacted with a nickel-containing compound to obtain a nickel complex shown in formula (I-5).

4. The method according to claim 3, characterized in that: The nickel-containing compound is selected from nickel-containing halides; The reaction is carried out under anaerobic conditions; The molar ratio of the nickel-containing compound to the compound represented by formula (II) is 1:1-2; The reaction temperature is 0-35 o C; the reaction time is 8-16 hours; The reaction is carried out in an organic solvent, and the organic solvent is selected from one or more of halogenated alkanes or alcohol solvents.

5. A method for preparing a compound of the structure represented by formula (II-5) in claim 1, comprising the following steps: 1) reacting aniline represented by formula (III) with AlMe3 to obtain a reaction solution containing a secondary amine structure connected by an aluminum bridge represented by formula (IV); 2) Adding (D,L)-camphorquinone represented by formula (V) to the reaction solution in step 1) for condensation reaction to obtain a compound represented by formula (II-5); Formula (III) Formula (IV) Formula (V); In formula (III) and formula (IV), R 1 = (p-FPh)2CH-; R 2 = Me; In formula (V), R 3 = Me.

6. A catalyst composition comprising a main catalyst and a co-catalyst, wherein: The main catalyst is a nickel complex represented by formula (I-5) in claim 2; The co-catalyst is selected from one or more of aluminoxane, alkylaluminum and alkylaluminum chloride.

7. The catalyst composition according to claim 6, characterized in that: The aluminoxane is selected from one or both of methylaluminoxane and triisobutylaluminum-modified methylaluminoxane; The alkyl aluminum is selected from one or two of trimethyl aluminum, triethyl aluminum or triisobutyl aluminum; The alkylaluminum chloride is selected from one or more of ethylaluminum dichloride, diethylaluminum chloride, and dimethylaluminum chloride; The molar ratio of the metal Al in the co-catalyst to the central metal Ni of the nickel complex represented by formula (I) is (100-4000):

1.

8. Use of the nickel complex represented by formula (I-5) in claim 2 or the catalyst composition described in claim 6 or 7 in catalyzing olefin polymerization.

9. The use according to claim 8, characterized in that: The nickel complex represented by formula (I-5) in claim 2 or the catalyst composition described in claim 6 or 7 is used to catalyze ethylene polymerization reaction.

10. A method for preparing polyethylene, comprising polymerizing ethylene under the action of the catalyst composition according to claim 6 or 7 to obtain polyethylene.

11. The method according to claim 10, characterized in that: The polymerization temperature is 30-90°C; The polymerization reaction time is 5 to 120 min; The polymerization reaction is carried out in a solvent, and the solvent is selected from one or more of toluene, dichloromethane, ethanol, tetrahydrofuran, hexane or cyclohexane; The polymerization reaction was carried out under ethylene atmosphere.

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