Acenaphthene-based α-diimine nickel complex, catalyst and application thereof

Abstract

The present invention provides an acenaphthyl α-diimine nickel complex, a catalyst and its application. The catalyst provided by the present invention has the characteristics of high catalytic activity and stable performance in olefin polymerization, especially in ethylene polymerization. The acenaphthyl α-diimine nickel complex has multiple catalytic active centers, and the selective expression of its active centers can be changed by regulating the polymerization conditions, and it can generate single-peak or bimodal polyethylene. Based on the catalyst of the present invention, an olefin polymer with high molecular weight and macroscopically adjustable molecular weight can be prepared. The acenaphthyl α-diimine nickel complex has the structure shown in the following structural formula (I): wherein, R<supgt;1< / supgt>, R<supgt;2< / supgt>, R<supgt;3< / supgt> are the same or different and are independently selected from hydrogen, methyl, ethyl or isopropyl; each X is the same or different and is independently selected from F, Cl, Br or I; Φ represents

Description

Technical Field

[0001] The invention belongs to the technical field of olefin catalytic polymerization, and specifically relates to an acenaphthene-based alpha-diimine nickel complex, a catalyst and application thereof. Background Art

[0002] Polyethylene is the fastest growing, largest-yield and most widely used synthetic resin. It is widely used in many fields such as industry, agriculture, military, medical care, daily life, etc. The extensive development and application of polyethylene products are inseparable from the development of olefin polymerization catalysts. At present, the industrialized polyethylene catalysts mainly include Ziegler-Natta catalysts, Phillips catalysts and metallocene catalysts, as well as the late transition metal complex type high-efficiency ethylene polymerization and polymerization catalysts that have been rapidly developed in recent years.

[0003] In 1995, Brookhart and his colleagues reported a class of α-diimine Ni (II) and Pd (II) complexes (A and B, Formula 1), which were proven to be highly efficient catalysts for the polymerization of ethylene, α-olefins and certain functional polar olefins (J.Am.Chem.Soc., 1995, 117, 6414). This discovery has a milestone significance in the history of olefin catalyst development. However, the classic Brookhart type α-diimine nickel complexes have the defects of insufficient thermal stability, low catalytic activity and poor polymer performance at industrial operating temperatures (80-100°C). Since then, scholars in the scientific and industrial circles have conducted a lot of research on improving the thermal stability of α-diimine nickel catalysts, and directly synthesizing branched elastomeric materials by ethylene homopolymerization.

[0004]

[0005] The inventor's research group has been committed to the design and development of olefin polymerization catalysts and the exploration of catalytic processes, and has carried out a lot of exploration and structural optimization work around N^N, N^N^N, and N^O type late transition metal catalysts. Among them, 4,5-diazafluorene-9-one benzoylhydrazone nickel complex uses MAO as a co-catalyst and can catalyze ethylene polymerization well at normal pressure, with an activity of 10 4 ~10 5 g(PE)mol(Ni) -1 h -1 (Appl. Catal., A, 2003, 246, 11), and its structural formula is shown in Formula 2;

[0006]

[0007] Subsequently, mononuclear (Formula 3) and binuclear (Formula 4) pyridine imine nickel complexes were designed and synthesized, and both can catalyze ethylene oligomerization and polymerization to obtain oligomers and low molecular weight branched polyethylene with branched chains mainly composed of butyl groups (J. Organomet. Chem. 2005, 690, 1570 and J. Organomet. Chem., 2005, 690, 1739);

[0008]

[0009] Another type of polymerization catalyst, 2-benzimidazole-1,10-phenanthroline nickel complex (Formula 5), ​​has a catalytic activity of 1.27×10 7 g·mol -1 ·h -1 (Eur. J. Inorg. Chem. 2007, 3816), which is significantly higher than the catalytic activity of other catalysts in ethylene production.

[0010] The catalysts mentioned above have only the ability to polymerize or prepare low molecular weight polymers, and cannot prepare high molecular weight, high branching degree polyethylene elastomer materials. In recent years, the inventors have systematically modified the structure of acenaphthenequinone-based asymmetric α-diimine nickel complexes (shown in Formula 6). This type of nickel catalyst has better thermal stability, shows high ethylene polymerization activity and can obtain polyethylene elastomer materials. The R and R' groups are easy to modify, which is conducive to the precise regulation of the microstructure of the polymerization product. It is an ideal candidate catalyst for the industrial production of ethylene (Coord. Chem. Rev. 2017, 350, 68–83).

[0011]

[0012] At present, the α-diimine catalysts used for olefin polymerization still have the problem that the molecular weight of polyethylene produced at high operating temperatures is too low, resulting in a narrow application range. At the same time, if this type of catalyst is to be industrialized, there are still difficulties in related basic research and constraints on promoting industrialization. It is still an urgent problem to develop catalysts with good thermal stability and high activity for catalyzing olefin polymerization, so as to prepare branched polyethylene with high degree of branching, high molecular weight, macroscopically controllable molecular weight distribution, and thus good mechanical properties. Summary of the invention

[0013] In view of this, the present invention provides an acenaphthene-based α-diimine nickel complex and its intermediates, as well as respective preparation methods, and also provides a catalyst obtained based on the acenaphthene-based α-diimine nickel complex and its application. The catalyst provided by the present invention has the characteristics of high catalytic activity and stable performance in olefin polymerization, especially ethylene polymerization, wherein the acenaphthene-based α-diimine nickel complex has multiple catalytic active centers, and the selective expression of its active centers can be changed by regulating the polymerization conditions, and unimodal or bimodal polyethylene can be generated. Based on the catalyst of the present invention, an olefin polymer with high molecular weight and macroscopically controllable molecular weight can be obtained.

[0014] To achieve the purpose, the present invention provides the following technical solutions:

[0015] The first aspect of the present invention provides an acenaphthene-based α-diimine nickel complex, wherein the acenaphthene-based α-diimine nickel complex has a structure shown in the following structural formula (I):

[0016]

[0017] Among them, R 1 , R 2 , R 3 are the same or different and are independently selected from hydrogen, methyl, ethyl or isopropyl;

[0018] Each X is the same or different and is independently selected from F, Cl, Br or I;

[0019] Φ represents

[0020] The present inventors have found that by modifying the ortho-para substituents of the N-aryl group and introducing "methoxy" and "trifluoromethoxy", a highly active catalyst with better stability in olefin polymerization can be obtained and high molecular weight polyethylene can be successfully produced.

[0021] In some preferred embodiments, the acenaphthenyl α-diimine nickel complex has a structure shown in the following structural formula (I-1), (I-2), (I-3), (I-4), (I-5) or (I-6):

[0022]

[0023] The second aspect of the present invention provides an intermediate of an acenaphthene-based α-diimine nickel complex, wherein the intermediate has a structure shown in the following structural formula (II):

[0024]

[0025] Among them, R 1 , R 2 , R 3and Φ have the definitions described above; specifically, R 1 , R 2 , R 3 are the same or different and are independently selected from hydrogen, methyl, ethyl or isopropyl; Φ represents

[0026] In some preferred embodiments, the intermediate has a structure shown by the following structural formula (II-1), (II-2), (II-3), (II-4), (II-5) or (II-6):

[0027]

[0028] The third aspect of the present invention provides an acenaphthene imide compound, wherein the acenaphthene imide compound has a structure shown in the following structural formula (III):

[0029]

[0030] Among them, Φ represents

[0031] A fourth aspect of the present invention provides an aniline compound, wherein the aniline compound has a structure shown in the following structural formula (IV):

[0032]

[0033] Among them, Φ represents

[0034] The fifth aspect of the present invention provides a method for preparing the acenaphthene-based α-diimine nickel complex having the structural formula (I) as described above, the preparation method comprising: reacting the intermediate of the structural formula (II) as described above with a nickel-containing compound (e.g., a complexation reaction) to obtain the acenaphthene-based α-diimine nickel complex of the structural formula (I) as described above;

[0035] Preferably, the nickel-containing compound is selected from nickel-containing halides; for example, it may be one or more of (DME)NiBr2, NiCl2·6H2O, NiBr2, preferably (DME)NiBr2 or NiCl2·6H2O.

[0036] Preferably, the reaction is carried out under oxygen-free conditions, specifically, for example, the reaction is carried out in a protective gas atmosphere, and the protective gas is, for example, nitrogen or other gas inert to the reaction.

[0037] Preferably, the molar ratio of the nickel-containing compound to the intermediate of the structural formula (II) is 2:(2-3), preferably 2:(2-2.5), and more preferably 2:2.1.

[0038] Preferably, the reaction temperature is 0-35°C, preferably 10-30°C, more preferably 20-25°C; the reaction time is preferably 8-16 hours, more preferably 12-16 hours.

[0039] Preferably, the reaction is carried out in an organic solvent, and the organic solvent is preferably selected from one or more cyclic ether solvents, more preferably tetrahydrofuran.

[0040] Preferably, the method further comprises a step of purifying the reaction product; further preferably, the purification comprises the following operations: removing the solvent from the reaction product, for example, by extracting the solvent through a vacuum pump, then dissolving the reaction product in an organic solvent and precipitating the precipitate, washing the obtained solid phase with anhydrous ether after solid-liquid separation, and then drying; wherein the organic solvent is preferably anhydrous ether.

[0041] The sixth aspect of the present invention provides a method for preparing the intermediate having structural formula (II) as described above, the preparation method comprising:

[0042] 1) stirring the acenaphthene imide compound of the above-mentioned structural formula (III), a water-soluble zinc salt and a substituted aniline compound of the structural formula (V) in the presence of an organic acid to obtain an intermediate product (an α-diimine zinc complex intermediate);

[0043] Where R 1 , R 2 , R 3 has the definition as set out above;

[0044] 2) adding the intermediate product into an organic solvent and adding a 2+ Stably combining to form a complex with an aqueous solution of a weak salt, stirring the reaction, and separating the organic layer to obtain the intermediate of structural formula (II); the weak salt is preferably one or more of carbonate, bicarbonate, and oxalate;

[0045] Preferably, in step 1), the organic acid is a carboxylic acid, preferably one or more selected from formic acid, acetic acid, oxalic acid or succinic acid, more preferably acetic acid;

[0046] Preferably, in step 1), the molar volume ratio of the acenaphthene imide compound of structural formula (III) to the organic acid is 2 mmol:(1-7) mL, which means that the amount of organic acid used is 1-7 mL for every 2 mmol of the acenaphthene imide compound of structural formula (III); preferably, the molar volume ratio is 2 mmol:(2-5) mL, more preferably 2 mmol:3 mL.

[0047] Preferably, in step 1), the molar ratio of the acenaphthene imide compound of formula (III) to the substituted aniline compound of formula (V) is 2:(2-6), preferably 2:(2-4), and more preferably 2:(2-3).

[0048] Preferably, in step 1), the molar ratio of the imine acenaphthene compound of structural formula (III) to the water-soluble zinc salt is 2:(2-4), preferably 2:(2-3), and more preferably 2:(2-2.5);

[0049] Preferably, in step 1), the reaction is carried out under heating reflux, preferably at a reaction temperature of 60-150° C., more preferably 105-135° C., and a reaction time of 2-6 h, more preferably 4-5 h;

[0050] Preferably, in step 2), the 2+ The molar ratio of the weak acid ions and the water-soluble zinc salt in the weak acid salt aqueous solution combining to form the complex is (2.2-4.5):2.2, more preferably (3.2-4.5):2.2, and more preferably 4.4:2.2; wherein the weak acid ions are carbonate ions, bicarbonate ions and / or oxalate ions, and when multiple of these ions are present, the molar amount of the weak acid ions in the aforementioned molar ratio is the total molar amount of each weak acid ion contained; preferably, the weak acid salt is selected from one or more of potassium carbonate, potassium bicarbonate, and potassium oxalate;

[0051] Preferably, in step 2), the organic solvent is selected from one or more halogenated alkane solvents, preferably one or more of methyl chloride, dichloromethane, dichloroethane, chloroform, more preferably dichloromethane;

[0052] Preferably, in step 2), the reaction temperature is 15-30°C, preferably 20-25°C, and the reaction time is 1-3h, preferably 1-1.5h;

[0053] In some embodiments, the water-soluble zinc salt may be one or more of zinc chloride, zinc sulfate, zinc acetate, etc., preferably zinc chloride.

[0054] Preferably, the method further comprises a step of purifying the reaction product obtained in step 2), and the purification preferably comprises the following operations: removing the solvent from the reaction product obtained in step 2), for example, removing the solvent by a rotary evaporator, dissolving it in dichloromethane, adding an alkane organic solvent to recrystallize and precipitate, performing solid-liquid separation, washing the obtained solid phase with an alkane and drying it, wherein the alkane is preferably n-hexane.

[0055] The seventh aspect of the present invention provides a method for preparing the acenaphthene imide compound having the structural formula (III) as described above, the preparation method comprising: reacting the aniline compound (2-[(2,6-bis(bis(4-methoxyphenyl)methyl)-4-(trifluoromethoxy)aniline) of the structural formula (IV) as described above and acenaphthene-1,2-dione under the catalysis of an organic acid to obtain the acenaphthene imide compound of the structural formula (III);

[0056] Preferably, the reaction is carried out in the presence of an organic solvent, and the organic solvent is preferably selected from one or more of methanol, ethanol, and toluene, more preferably methanol;

[0057] Preferably, the organic acid is selected from one or more of formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid, more preferably p-toluenesulfonic acid;

[0058] Preferably, the molar ratio of the acenaphthene-1,2-dione to the organic acid is 2:(1-4), preferably 2:(1-2), more preferably 2:(1-1.5);

[0059] Preferably, the molar ratio of the acenaphthene-1,2-dione to the aniline compound of the structural formula (IV) is 2:(2-3), preferably 2:(2-2.5), more preferably 2:2;

[0060] Preferably, the reaction temperature of the reaction is 0-30°C, more preferably 20-25°C, and the reaction time is preferably 12-36h, more preferably 20-24h;

[0061] Preferably, the method further comprises a step of purifying the reaction product; preferably, the purification operation comprises: performing solid-liquid separation on the reaction product, such as filtering for solid-liquid separation under normal pressure, dissolving the obtained solid phase in an organic solvent, then adding methanol for recrystallization to precipitate, and drying the obtained solid phase after solid-liquid separation; preferably, the organic solvent is dichloromethane.

[0062] The eighth aspect of the present invention provides a catalyst, which comprises a main catalyst and an optional co-catalyst; the main catalyst is selected from one or more of the acenaphthene-based α-diimine nickel complexes of structural formula (I) described above;

[0063] Preferably, the cocatalyst is selected from one or more of aluminoxane, alkylaluminum and alkylaluminum chloride; more preferably, the aluminoxane is selected from methylaluminoxane (MAO) and / or triisobutylaluminum-modified methylaluminoxane (MMAO), and methylaluminoxane is further preferred; more preferably, the alkylaluminum chloride is selected from one or more of diethylaluminum monochloride (DEAC), triethylaluminum trichloride (EASC) or ethylaluminum dichloride (EADC), and diethylaluminum monochloride is further preferred;

[0064] Preferably, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (300-3500):1;

[0065] Further preferably, when the co-catalyst is aluminoxane, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (1500-3500):1, more preferably 2900-3100:1, for example 3000:1;

[0066] Further preferably, when the co-catalyst is alkylaluminum chloride, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (300-700):1, more preferably 550-650:1, for example 600:1.

[0067] The present invention also provides the use of the catalyst described above in olefin polymerization reaction;

[0068] Preferably, the olefin polymerization reaction is ethylene polymerization reaction.

[0069] The present invention further provides a method for preparing polyethylene, wherein the catalyst described above is used to catalyze the polymerization reaction of ethylene to prepare the polyethylene;

[0070] Preferably, the reaction temperature of the polymerization reaction is 20-80°C, for example, 20°C, 30°C, 40°C, 60°C, 80°C, etc.; the reaction time is preferably 5-120min, for example, 5min, 15min, 30min, 45min, 60min, 100min, 120min, etc.; the reaction pressure is preferably 0.3-20atm, for example, 1atm, 5atm or 10atm, etc.

[0071] The solvent used in the above polymerization reaction may be, for example, one or more of toluene, o-xylene, n-hexane or cyclohexane.

[0072] The technical solution provided by the present invention has the following beneficial effects:

[0073] 1. The present invention provides a method for preparing a remote methoxy-substituted acenaphthenyl α-diimine nickel complex containing a trifluoromethoxy group, which has the advantages of mild reaction conditions, short reaction cycle, simple operating conditions, etc.

[0074] 2. The acenaphthene-based α-diimine nickel complex provided by the present invention has the advantages of high catalytic activity, low cost, stable performance, etc. in catalyzing ethylene polymerization. In ethylene polymerization, at 30°C, using Et2AlCl as a co-catalyst, the activity of the nickel complex in catalyzing ethylene polymerization can reach 3.35×10 7 g·mol -1 (Ni)·h -1, is one of the catalysts with the highest catalytic activity at present. After one hour of polymerization, the activity is still as high as 1.38×10 7 g(PE)mol -1 (Ni)h -1 In addition, the catalyst system has good thermal stability. At an operating temperature of 80°C, the catalytic activity is still excellent and can be maintained at 8.74×10 6 g(PE)mol -1 (Ni)h -1 .

[0075] 3. The acenaphthene-based α-diimine nickel complex provided by the present invention can be used as an olefin polymerization catalyst, has multiple catalytic active centers, and can change the selective expression of the first and second active centers by regulating the polymerization conditions to generate unimodal or bimodal polyethylene. The favorable conditions for the generation of bimodal polyethylene are high temperature (Example 14i), high concentration of cocatalyst (Example 14d) or the use of Et2AlCl cocatalyst (Example 22).

[0076] 4. The polymer obtained by catalyzing olefin polymerization with the acenaphthene-α-diimine nickel complex provided by the present invention has a high molecular weight and is macroscopically controllable. The molecular weight of polyethylene is controlled by changing the ortho-substituents. The greater the steric hindrance of the ortho-substituents in the catalytic system, the higher the molecular weight; the molecular weight of polyethylene is controlled by changing the reaction conditions. In the catalytic system, the molecular weight gradually decreases with the increase of temperature and gradually increases with the extension of the polymerization reaction time; the molecular weight of polyethylene is controlled by changing the type of co-catalyst. In some embodiments, the molecular weight Mw of polyethylene obtained by using MMAO as a co-catalyst in the catalytic system is (2.73-16.84)×10 5 g·mol -1 , Et2AlCl as a co-catalyst to obtain polyethylene with a molecular weight of (3.64-13.62)×10 5 g·mol -1 .

[0077] 5. The branching degree of the polymer obtained by catalyzing olefin polymerization with the acenaphthene-based α-diimine nickel complex provided by the present invention can be controlled. It has high selectivity for short-chain methyl branches and a wide range of controllable branching degree, ranging from (16-101) branches per 1000 carbon atoms.

[0078] 6. The acenaphthene-α-diimine nickel complex provided by the present invention can catalyze ethylene polymerization to produce two types of polymers; wherein the Ni / MMAO system can produce semi-crystalline unimodal polyethylene under certain polymerization conditions, and in some embodiments, the obtained polyethylene has a X c =43.7%. The obtained polyethylene in the Ni / Et2AlCl system is a nearly amorphous bimodal polyethylene. In some embodiments, the obtained polyethylene has a X c=1.3%,4.7%. The latter (bimodal polyethylene) has good mechanical properties, and the polyethylene elastomer with good mechanical properties is obtained, which has great industrial application potential.

[0079] The mechanical properties of the nearly amorphous bimodal polyethylene obtained in the Ni / Et2AlCl system are related to the molecular weight. The polyethylene with a large molecular weight exhibits better tensile strength. In some embodiments, the Mw of the polyethylene prepared by catalyst Ni5 is 8.32×10 5 g·mol -1 The tensile strength of polyethylene can reach 20.3MPa and the elongation at break can reach 892%. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 This is a schematic diagram of the molecular structure of single crystal Ni1 analyzed in Example 8 of the present invention.

[0081] Figure 2 This is a schematic diagram of the molecular structure analyzed from a single crystal of Ni4 in Example 11 of the present invention.

[0082] Figure 3 This is the temperature-elevated NMR carbon spectrum of the polyethylene obtained in Example 14a).

[0083] Figure 4 This is the temperature-elevated NMR carbon spectrum of the polyethylene obtained in Example 22a).

[0084] Figure 5 This is the temperature-raising NMR carbon spectrum of the polyethylene obtained in Example 23.

[0085] Figure 6 This is the temperature-raising NMR carbon spectrum of the polyethylene obtained in Example 27.

[0086] Figure 7 22a), f), h) and Example 26.

[0087] Figure 8 The elastic recovery curves of the polyethylene samples obtained in Examples 22a), f), h) and 26. DETAILED DESCRIPTION

[0088] In order to facilitate the understanding of the present invention, the present invention will be further described below in conjunction with examples. It should be understood that the following examples are only for a better understanding of the present invention and do not mean that the present invention is limited to the following examples.

[0089] As a preferred embodiment, the synthesis of the complexes in the following examples is carried out according to the following reaction path:

[0090]

[0091] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0092] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0093] Unless otherwise specified, the concentrations in the following examples are molar concentrations.

[0094] The molecular weight and molecular weight distribution of the polymers obtained in the following ethylene polymerization examples were determined by conventional high temperature GPC methods. The melting point and crystallinity (X c ) were determined by conventional DSC methods, and the polymerization activity of the polymers was calculated according to the following formula: polymerization activity = polymer yield / (catalyst dosage*polymerization time). The branching degree was determined by taking 50 mg of the corresponding polymer, dissolving it in 5 mL of deuterated o-dichlorobenzene, and measuring it at 110°C. 13 C NMR data were used to calculate the fracture strain and ultimate tensile stress. The fracture strain and ultimate tensile stress were obtained by measuring the stress-strain curve data of the sample strip at fracture at room temperature. The elastic recovery rate (SR) was obtained by measuring the DMA curve data at room temperature.

[0095] The structures of all the synthesized compounds described below were confirmed by nuclear magnetic resonance analysis and elemental analysis.

[0096] In Example 1, the specific method for preparing the aniline compound (2-[(2,6-bis(bis(4-methoxyphenyl)methyl)-4-(trifluoromethoxy)aniline) of structural formula (IV) is as follows: 4,4-dimethoxybenzhydrol (9.77 g, 40 mmol) and p-trifluoromethoxyaniline (3.54 g, 20 mmol) were placed in a 250 mL round-bottomed flask. The mixture was stirred and heated to 120° C., and then a catalyst of zinc chloride (1.36 g, 10 mmol) and p-toluenesulfonic acid (10 mmol) were added to the reaction solution. The reaction mixture was stirred and heated to 120° C. The mixture was further refluxed and stirred at 120°C for 2 hours. After cooling to room temperature, the catalyst solid in the solution was filtered, and the solvent was removed using a rotary evaporator. The residue was dissolved in dichloromethane (100 mL), washed with a saturated aqueous solution of ammonium chloride (2×30 mL), and then washed with a saturated aqueous solution of sodium chloride (30 mL). The organic phase was then dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. 20 ml of methanol was then added, and the residue was purified using an ultrasonic instrument to assist recrystallization to obtain 9.82 g of white powder. Yield: 78%.

[0097] The structural confirmation data are as follows:

[0098] 1H NMR (CDCl3, 400MHz, TMS): δ7.11 (d, J = 7.7Hz, 8H), 6.96 (d, J = 7.9Hz, 8H), 6.62 (s, 2H), 5.33 (s, 2H), 3.89 (s, 12H).

[0099] 13 C NMR (CDCl3, 100MHz, TMS): δ158.29, 139.67, 135.32, 130.51, 129.91, 129.33, 128.81, 126.67, 113.97, 55.35, 50.86.

[0100] 19 F NMR (470 MHz, CDCl3): δ-58.07.

[0101] Elemental analysis: C 37 H 34 N (629.68) Theoretical value: C, 70.58; H, 5.44; N, 2.22. Exp. value: C, 70.51; H, 5.38; N, 2.07.

[0102] Example 1

[0103] The acenaphthene imide compound ((2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene) represented by formula (III) was prepared.

[0104] In a 250 mL round-bottom flask, an aniline compound of structural formula (IV) (2-[(2,6-bis(bis(4-methoxyphenyl)methyl)-4-(trifluoromethoxy)aniline)) (1.26 g, 2.0 mmol), acenaphthene-1,2-dione (0.37 g, 2.0 mmol) and 0.2 g of p-toluenesulfonic acid were added and dissolved in 100 ml of methanol solution. After the reaction was stirred at room temperature for 24 hours, the precipitated yellow precipitate was filtered to obtain a crude product. Then, the crude product was dissolved in 3 ml of dichloromethane, 20 ml of methanol was slowly added, and the crude product was purified by using an ultrasonic instrument to assist recrystallization, and 0.92 g of bright yellow powder was obtained by solid-liquid separation. Yield: 58%.

[0105] The structural confirmation data are as follows:

[0106] 1H NMR (CDCl3, 400MHz, TMS): δ8.05 (s, 2H), 7.74 (s, 2H), 7.06 (s, 1H), 6.94 (d, J = 7.2Hz, 5H), 6.87-6 .63(m,11H),6.08(d,J=7.1Hz,4H),5.93(d,J=6.5Hz,1H),5.34(s,2H),3.77(s,6H),3.25(s,6H).

[0107] 13 C NMR (CDCl3, 100MHz, TMS): δ189.48,162.79,158.17,157.27,146.70,145.66,142.39,134.37,133.27,131.80,130.50,130.18, 129.96,129.87,128.36,127.62,127.27,126.41,123.95,121.67,120.51,113.73,113.41,55.26,55.18,54.65,50.56,50.49.

[0108] 19 F NMR (470 MHz, CDCl3): δ-58.03.

[0109] Elemental analysis: C 49 H 38 N (793.84) Theoretical value: C, 74.14; H, 4.83; N, 1.76. Exp. value: C, 73.91; H, 4.88; N, 1.77.

[0110] Example 2

[0111] The intermediate of the acenaphthene-based α-diimine nickel complex (1-(2,4-dimethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene, denoted as ligand L1) is prepared as shown in formula (II), wherein R 1 is methyl, R 2 is hydrogen, R 3 It is methyl.

[0112] In a 100 ml round-bottom flask, 0.3 g of zinc chloride, the compound of formula (III) prepared in Example 1 ((2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene) (1.60 g, 2 mmol) and 2,4-dimethylaniline (0.30 g, 2.5 mmol) were added, and 3 ml of acetic acid was injected. After being mixed evenly, the mixed solution was kept under reflux at 130° C. and stirred for 4 hours. Once cooled to room temperature, a yellow precipitate (zinc chloride (II) complex solid) was obtained. The resulting yellow precipitate was passed through Filter and rinse with ether to obtain zinc chloride (II) complex. Add saturated potassium carbonate aqueous solution (potassium carbonate 4.4mmol, water 6mL) to dichloromethane solution (20mL) containing zinc chloride (II) complex, stir at room temperature for 1 hour, and separate the organic layer by extraction. After removing volatiles by rotary evaporation, dissolve the product with 5mL dichloromethane, slowly add 10mL n-hexane solution, and use ultrasonic instrument to assist recrystallization at room temperature to obtain ligand L1. After solid-liquid separation, dry the obtained solid phase to obtain 0.95g of yellow powder. Yield: 53%.

[0113] The structural confirmation data are as follows:

[0114] FT-IR(cm -1 ):2159(w),2027(w),1973(w),1668(w,vC=N),1640(w,vC=N),1607(w),1584

[0115] (w),1510(m),1438(w),1252(s),1218(w),1172(m),1110(w),1036(w),929(w),873(w),826(w),778(w),735(w).

[0116] 1H NMR (CDCl3, 400MHz, TMS): δ7.74 (d, J=8.0Hz, 1H, Ph-H), 7.65 (d, J=8.2Hz, 1H, Ph-H), 7.30 (t, J=7. 6Hz,1H,Ph-H),7.19-7.09(m,2H,Ph-H),7.00(d,J=7.7Hz,5H,Ph-H),6.82(d,J=13.5Hz,11H,Ph-H ),6.70(d,J=7.0Hz,1H,Ph-H),6.09(d,J=7.6Hz,4H,Ph-H),5.94(d,J=7.0Hz,1H,Ph-H),5.50(s,2 H,-CH(p-OMePh)2),3.77(s,6H,-OCH3),3.23(s,6H,-OCH3),2.43(s,3H,-CH3),2.24(s,3H,-CH3).

[0117] 13 C NMR(CDCl3,100MHz,TMS): δ163.91,160.83,158.00,157.10,147.95,147.51,14 5.18,140.14,134.75,134.53,133.69,133.36,131.48,130.60,130.23,129.89, 128.41,128.33,128.22,128.01,127.46,127.22,126.88,125.54,123.88,122.57,121.79,120.40,117.08,113.63,113.23,55.17,54.61,50.54,21.01,17.80.

[0118] 19 F NMR (470 MHz, CDCl3): δ-58.3.

[0119] Elemental analysis: C 57 H 47 N2 (897.01) theoretical value: C, 76.32; H, 5.28; N, 3.12. Exp. value: C, 75.98; H, 5.23; N, 3.13.

[0120] Example 3

[0121] The intermediate of the acenaphthene-based α-diimine nickel complex (1-(2,6-diethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene, denoted as ligand L2) is prepared as shown in formula (II), wherein R 1 Ethyl, R 2Ethyl, R 3 For hydrogen.

[0122] Ligand L2, 1.02 g, was prepared according to the method in Example 2, except that 2,4-dimethylaniline was replaced by an equal molar amount of 2,6-diethylaniline. Yield: 55%.

[0123] The structural confirmation data are as follows:

[0124] FT-IR(cm -1 ):3010(w),2952(w),1975(w),1670(w,v C＝N ),1650(w,v C＝N ),1607(w),

[0125] 1587(m),1508(s),1458(w),1436(w),1300(m),1244(s),1171(m),1106(m),1032(s),922(w),873(w),824(w),775(m),709(w).

[0126] 1 H NMR (CDCl3, 400MHz, TMS): δ7.72 (d, J=8.1Hz, 1H, Ph-H), 7.58 (d, J=8.2Hz, 1H, Ph-H), 7.28 (d, J=4.1Hz, 1H, Ph-H ),7.28-7.19(m,4H,Ph-H),7.05-6.91(m,5H,Ph-H),6.86(s,2H,Ph-H),6.80(d,J=8.4Hz,8H,Ph-H),6.56(d,J=7 .0Hz,1H,Ph-H),6.05(d,J=7.7Hz,4H,Ph-H),5.78(d,J=7.0Hz,1H,Ph-H),5.54(s,2H,-CH(p-OMePh)2),3.77(s ,6H,-OCH3),3.21(s,6H,-OCH3),2.76-2.66(m,2H,-CH2),2.59-2.50(m,2H,-CH2),1.19(t,J=7.4Hz,6H,-CH3).

[0127] 13C NMR(CDCl3,100MHz,TMS): δ164.05,161.53,158.11,157.17,148.14,147.55,1 45.28,139.81,134.91,134.79,133.25,130.57,130.26,129.69,128.71,128.5 3,127.91,127.70,127.33,126.91,126.23,124.20,122.33,121.83,120.59,119.30,113.66,113.36,55.25,55.18,54.63,50.58,50.52,24.50,14.38,14.35.

[0128] 19 F NMR (470 MHz, CDCl3): δ-58.05.

[0129] Elemental analysis: C 59 H 51 N2 (925.06) theoretical value: C, 76.61; H, 5.56; N, 3.03. Exp. value: C, 76.43; H, 5.42; N, 3.09.

[0130] Example 4

[0131] The intermediate of the acenaphthene-based α-diimine nickel complex (1-(2,6-diisopropylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene, denoted as ligand L3) is prepared as shown in formula (II), wherein R 1 is isopropyl, R 2 Isopropyl, R 3 For hydrogen.

[0132] Ligand L3 (1.09 g) was prepared according to the method in Example 2, except that 2,4-dimethylaniline was replaced by an equal molar amount of 2,6-diisopropylaniline. Yield: 57%.

[0133] The structural confirmation data are as follows:

[0134] FT-IR(cm -1 ):2957(w),2834(w),1667(w,v C＝N ),1643(w,v C＝N ),1608(w),1590(w),1508(s),

[0135] 1462 (w), 1438 (m), 1389 (w), 1331 (w), 1296 (w), 1249 (w), 1181 (w), 1107 (w), 1035 (w), 926 (w), 868 (w), 852 (w), 825 (m), 779 (w), 769 (w), 736 (w), 658 (w).

[0136] 1 1H NMR (CDCl3, 400 MHz, TMS): δ 7.71 (d, J = 8.1 Hz, 1H, Ph - H), 7.55 (d, J = 8.3 Hz, 1H, Ph - H), 7.30 (s, 3H, Ph - H), 7.24 (d, J = 7.8 Hz, 1H, Ph - H), 7.00 (d, J = 7.9 Hz, 4H, Ph - H), 6.94 - 6.85 (m, 3H, Ph - H), 6.80 (t, J = 8.6 Hz, 8H, Ph - H), 6.48 (d, J = 7.3 Hz, 1H, Ph - H), 6.02 (d, J = 7.7 Hz, 4H, Ph - H), 5.69 (d, J = 7.0 Hz, 1H, Ph - H), 5.54 (s, 2H, -CH(p - OMePh)2), 3.78 (s, 6H, -OCH3), 3.19 (s, 6H, -OCH3), 3.21 - 3.15 (m, 2H, -CH), 1.30 (d, J = 6.6 Hz, 6H, -CH3), 1.04 (d, J = 6.8 Hz, 6H, -CH3).

[0137] 13 13C NMR (CDCl3, 100 MHz, TMS): δ 164.26, 162.02, 158.06, 157.08, 147.58, 146.86, 145.25, 139.81, 135.57, 134.96, 134.85, 133.09, 130.57, 130.28, 129.57, 128.55, 128.50, 127.69, 127.55, 126.95, 126.87, 124.65, 124.32, 123.61, 122.93, 120.60, 113.59, 113.36, 55.22, 54.57, 50.48, 28.55, 24.18, 23.69.

[0138] 19 19F NMR (470 MHz, CDCl3): δ -58.07.

[0139] Elemental analysis: C 61 H 55N2 (953.12) theoretical value: C, 76.87; H, 5.82; N, 2.94. Exp. value: C, 75.97; H, 5.74; N, 2.94.

[0140] Example 5

[0141] The intermediate (1-(2,4,6-trimethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene of the acenaphthene α-diimine nickel complex of formula (II) is prepared, which is denoted as ligand L4. 1 is methyl, R 2 Methyl, R 3 It is methyl.

[0142] Ligand L4 (1.02 g) was prepared according to the method in Example 2, except that 2,4,6-trimethylaniline was used in place of 2,4-dimethylaniline in an equal molar amount. Yield: 56%.

[0143] The structural confirmation data are as follows:

[0144] FT-IR(cm -1 ):2833(w),2160(w),2029(w),1677(w,v C＝N ),1649(w,v C＝N ),1608(w),1585

[0145] (w),1509(s),1462(w),1431(w),1252(s),1218(m),1171(m),1110(w),1033(m),923(w),874(w),829(m),781(m),734(w),698(w).

[0146] 1H NMR (CDCl3, 400MHz, TMS): δ7.74 (d, J=8.3Hz, 1H, Ph-H), 7.61 (d, J=8.0Hz, 1H, Ph-H), 7.30 (t, J= 7.7Hz,1H,Ph-H),6.99(d,J=5.3Hz,7H,Ph-H),6.84(s,2H,Ph-H),6.80(d,J=7.8Hz,8H,Ph-H),6. 63(d,J=6.9Hz,1H,Ph-H),6.06(d,J=7.7Hz,4H,Ph-H),5.86(d,J=6.9Hz,1H,Ph-H),5.52(s,2H, -CH(p-OMePh)2),3.77(s,6H,-OCH3),3.21(s,6H,-OCH3),2.39(s,3H,-CH3),2.20(s,6H,-CH3).

[0147] 13 C NMR (CDCl3, 100MHz, TMS): δ164.07,161.51,158.13,157.21,147.58,146.63,145.29 ,139.81,134.83,134.76,133.36,133.11,130.66,130.28,129.79,129,14,129.09,1 28.86,128.53,128.09,127.89,127.59,126.89,124.49,124.13,121.87,120.54,119.32,113.73,113.36,55.27,55.20,54.66,50.66,50.60,20.96,20.89,18.14,18.09.

[0148] 19 F NMR (470 MHz, CDCl3): δ-58.05.

[0149] Elemental analysis: C 58 H 49 N2 (911.03) theoretical value: C, 76.47; H, 5.42; N, 3.07. Exp. value: C, 76.01; H, 5.40; N, 3.02.

[0150] Example 6

[0151] The intermediate of the acenaphthene-based α-diimine nickel complex (1-(2,6-diethyl-4-methylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene, denoted as ligand L5) is prepared as shown in formula (II), wherein R 1Ethyl, R 2 Ethyl, R 3 It is methyl.

[0152] L5, 0.88 g, was prepared according to the method of Example 2, except that 2,4-dimethylaniline was replaced by an equal molar amount of 2,6-diethyl-4-methylaniline. Yield: 47%.

[0153] The structural confirmation data are as follows:

[0154] FT-IR(cm -1 ):2834(w),2160(w),2026(w),1974(w),1670(w)(m,v C＝N ),1643(m,v C＝N ),

[0155] 1607(w),1590(w),1508(s),1465(w),1439(w),1297(m),1249(s),1175(s),1109(w),1034(w),925(w),874(w),829(m),774(m),737(w).

[0156] 1 H NMR (CDCl3, 400MHz, TMS): δ7.72 (d, J=8.3Hz, 1H, Ph-H), 7.57 (d, J=8.3Hz, 1H, Ph-H), 7.29 (d, J=7.5Hz, 1H, Ph-H), 7.04 (s, 2H, Ph- H),7.00(d,J=8.5Hz,4H,Ph-H),6.93(t,J=7.7Hz,1H,Ph-H),6.85(s,2H,Ph-H),6.79(dd,J=8.5,3.9Hz,8H,Ph-H),6.62(d,J=7.1 Hz,1H,Ph-H),6.03(d,J=8.4Hz,4H,Ph-H),5.75(d,J=7.1Hz,1H,Ph-H),5.53(s,2H,-CH(p-OMePh)2),3.77(s,6H-OCH3),3.20(s, 6H-OCH3),2.66(dq,J=15.1,7.7Hz,2H,-CH2),2.51(dq,J=14.9,7.5Hz,2H,-CH2),2.44(s,3H,-CH3),1.16(t,J=7.5Hz,6H,-CH3).

[0157] 13C NMR(CDCl3,100MHz,TMS): δ164.12,162.84,161.70,158.10,157.16,147.62,145.63,1 45.23,139.78,134.93,134.81,133.38,133.26,132.19,130.79,130.59,130.39,130.2 5,129.68,128.80,128.40,127.96,127.67,127.29,127.03,124.14,122.37,120.57,113.65,113.43,113.35,55.25,55.18,54.62,50.57,50.51,24.48,21.22,21.16,14.47.

[0158] 19 F NMR (470 MHz, CDCl3): δ-58.06.

[0159] Elemental analysis: C 60 H 53 N2 (939.09) theoretical value: C, 76.74; H, 5.69; N, 2.98. Exp. value: C, 76.64; H, 5.62; N, 2.54.

[0160] Example 7

[0161] The intermediate of the acenaphthene-based α-diimine nickel complex (1-(2,6-dimethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene, denoted as ligand L6) is prepared as shown in formula (II), wherein R 1 is methyl, R 2 Methyl, R 3 For hydrogen.

[0162] L6, 0.91 g, was prepared according to the method of Example 2, except that 2,4-dimethylaniline was replaced by an equal molar amount of 2,6-dimethylaniline. Yield: 51%.

[0163] The structural confirmation data are as follows:

[0164] FT-IR(cm -1 ):2835(w),2156(w),1668(w,v C＝N ),1647(w,v C＝N ),1608(w),1583(w),1509

[0165] (m), 1463(w), 1440(w), 1356(w), 1302(m), 1247(s), 1226(w), 1175(m), 1153(w), 1109(w), 1035(w), 1009(w), 986(w), 924(w), 874(w), 828(w), 774(w), 740(w), 698(w), 657(w).

[0166] 1 1H NMR (CDCl3, 400 MHz, TMS): δ 7.74 (d, J = 8.2 Hz, 1H, Ph - H), 7.62 (d, J = 8.3 Hz, 1H, Ph - H), 7.29 (d, J = 7.6 Hz, 1H, Ph - H), 7.18 (d, J = 7.5 Hz, 2H, Ph - H), 7.14 - 7.06 (m, 1H, Ph - H), 7.00 (d, J = 8.5 Hz, 5H, Ph - H), 6.86 (s, 2H, Ph - H), 6.80 (dd, J = 8.5, 3.1 Hz, 8H, Ph - H), 6.57 (d, J = 7.1 Hz, 1H, Ph - H), 6.07 (d, J = 8.4 Hz, 4H, Ph - H), 5.88 (d, J = 7.1 Hz, 1H, Ph - H), 5.52 (s, 2H, -CH(p - OMePh)2), 3.77 (s, 6H, -OCH3), 3.21 (s, 6H, -OCH3), 2.24 (s, 6H, -CH3).

[0167] 13 13C NMR (CDCl3, 100 MHz, TMS): δ 163.95, 161.30, 158.08, 157.17, 149.07, 147.45, 145.28, 139.77, 134.77, 134.69, 133.29, 130.60, 130.22, 129.74, 128.70, 128.61, 128.36, 127.97, 127.87, 127.55, 126.88, 124.66, 124.12, 123.83, 121.81, 120.50, 119.26, 113.68, 113.32, 55.21, 55.14, 54.61, 50.61, 50.56, 18.15, 18.10.

[0168] 19 19F NMR (470 MHz, CDCl3): δ -58.04.

[0169] Elemental analysis: C 57 H 47N2 (897.01) theoretical value: C, 76.74; H, 5.69; N, 2.98. Exp. value: C, 76.64; H, 5.62; N, 2.54.

[0170] Example 8

[0171] Preparation of acenaphthenyl α-diimine nickel complex ([1-(2,4-dimethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene] nickel bromide, denoted as Ni1) shown in formula (I), wherein R 1 is methyl, R 2 is hydrogen, R 3 It is methyl.

[0172] At room temperature, (DME)NiBr2 (ethylene glycol dimethyl ether nickel bromide) (0.06 g, 0.2 mmol) and the ligand L1 prepared in Example 2 (0.19 g, 0.21 mmol) were mixed and dissolved in tetrahydrofuran, and stirred for 12 h under nitrogen protection. After the tetrahydrofuran was removed under reduced pressure, anhydrous ether was added to induce precipitation, from which a red solid was precipitated. The solid was filtered, washed with anhydrous ether, and dried to obtain a red solid complex. Yield: 81%.

[0173] The structural confirmation data are as follows:

[0174] FT-IR(cm -1 ):2160(w),2027(w),1970(w),1651(w,v C＝N ),1607(m),1586(m),1508(s),

[0175] 1463(w),1439(m),1387(w),1333(w),1290(w),1248(s),1219(s),1176(s), 1157(s),1033(m),960(w),874(w),831(s),775(m),736(w),697(w),659(w).

[0176] 19 F NMR (470MHz,CDCl3):δ-57.99.

[0177] Elemental analysis: C 57 H 47 N2 (1115.51) theoretical value: C, 61.37; H, 4.25; N, 2.51. Exp. value: C, 61.26; H, 4.41; N, 2.72.

[0178] The ether was diffused into the dichloromethane solution of the complex by slow diffusion at room temperature to grow a Ni1 single crystal suitable for X-ray measurement. In order to express more clearly, all hydrogen atoms in the molecular structure of the complex were not drawn when drawing with ORTEP. The perspective view of the crystal molecular structure is shown in Figure 1 As shown, it has a symmetrical structure, and the coordinated atoms exhibit a distorted tetrahedral geometry around the nickel center.

[0179] Example 9

[0180] Preparation of acenaphthenyl α-diimine nickel complex ([1-(2,6-diethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene] nickel bromide, denoted as Ni2) shown in formula (I), wherein R 1 Ethyl, R 2 Ethyl, R 3 For hydrogen.

[0181] Ni2 was prepared according to the method of Example 8, except that an equal molar amount of L2 prepared in Example 3 was used to replace L1. Yield: 77%.

[0182] The structural confirmation data are as follows:

[0183] FT-IR(cm -1 ):2965(w),1975(w),1647(w,v C＝N ),1608(m),1582(m),1508(s),1444(w),

[0184] 1425(w),1330(m),1298(w),1247(s),1206(w),1170(s),1111(m),1031(s),958(w),874(w),830(w),815(m),774(m),736(w),664(w).

[0185] 19 F NMR (470 MHz, CDCl3): δ-57.04.

[0186] Elemental analysis: C 61 H 55 N2 (1143.56) theoretical value: C, 61.97; H, 4.50; N, 2.45. Exp. value: C, 62.03; H, 4.87; N, 2.24.

[0187] Example 10

[0188] Preparation of acenaphthenyl α-diimine nickel complex ([1-(2,6-diisopropylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene] nickel bromide, denoted as Ni3) shown in formula (I), wherein R 1 is isopropyl, R 2 Isopropyl, R 3 For hydrogen.

[0189] Ni3 was prepared according to the method of Example 8, except that an equal molar amount of L3 prepared in Example 4 was used to replace L1. Yield: 79%.

[0190] The structural confirmation data are as follows:

[0191] FT-IR(cm -1 ):2961(w),2833(w),2160(w),1646(w,v C＝N ),1610(m),1583(m),1508(s),

[0192] 1465(w),1440(m),1385(w),1361(w),1295(w),1249(s),1205(m),1174(s),1110(w) ,1032(w),957(w),936(w),873(w),850(w),830(s),771(m),735(w),697(w),656(w).

[0193] 19 F NMR (470 MHz, CDCl3): δ-56.96.

[0194] Elemental analysis: C 61 H 55 N2 (1171.62) theoretical value: C, 62.54; H, 4.73; N, 2.39. Exp. value: C, 62.25; H, 4.77; N, 2.34.

[0195] Embodiment 11

[0196] Preparation of acenaphthenyl α-diimine nickel complex ([1-(2,4,6-trimethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene] nickel bromide, denoted as Ni4) shown in formula (I), wherein R 1 is methyl, R 2 Methyl, R 3 It is methyl.

[0197] Ni4 was prepared according to the method of Example 8, except that an equal molar amount of L4 prepared in Example 5 was used to replace L1. Yield: 76%.

[0198] The structural confirmation data are as follows:

[0199] FT-IR(cm -1 ):2833(w),2161(w),2035(w),1645(w,v C＝N ),1610(m),1583(m),1508(s),

[0200] 1462(w),1438(w),1383(w),1347(w),1299(m),1245(s),1175(s),1151(m), 1032(m),966(w),936(w),875(w),830(m),771(m),734(w),693(w),660(w).

[0201] 19 F NMR (470 MHz, CDCl3): δ-57.10.

[0202] Elemental analysis: C 58 H 49 N2 (1129.54) theoretical value: C, 61.67; H, 4.37; N, 2.48. Exp. value: C, 61.70; H, 4.13; N, 2.35.

[0203] The ether was diffused into the dichloromethane solution of the complex by slow diffusion at room temperature to grow a Ni4 single crystal suitable for X-ray measurement. In order to express more clearly, all hydrogen atoms in the molecular structure of the complex were not drawn when drawing with ORTEP. The perspective view of the crystal molecular structure is shown in Figure 2 As shown, it has a symmetrical structure, and the coordinated atoms exhibit a distorted tetrahedral geometry around the nickel center.

[0204] Example 12

[0205] Preparation of acenaphthenyl α-diimine nickel complex ([1-(2,6-diethyl-4-methylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene] nickel bromide, denoted as Ni5) shown in formula (I), wherein R 1 Ethyl, R 2 Ethyl, R 3 It is methyl.

[0206] Ni5 was prepared according to the method in Example 8, except that an equal molar amount of L5 prepared in Example 6 was used to replace L1. Yield: 83%.

[0207] The structural confirmation data are as follows:

[0208] FT-IR(cm -1 ):2835(w),1888(w),1642(m,v C＝N ),1611(w),1584(w),1508(s),1460(w),

[0209] 1441(w),1337(w),1296(m),1253(s),1174(s),1111(w),1030(w),965(w),868(w),825(m),772(m),730(w),695(w).

[0210] 19 F NMR (470 MHz, CDCl3): δ-57.06.

[0211] Elemental analysis: C 60 H 53 N2 (1157.59) theoretical value: C, 62.26; H, 4.62; N, 2.42. Exp. value: 62.31; H, 4.57; N, 2.45.

[0212] Embodiment 13

[0213] Preparation of acenaphthene-based α-diimine nickel complex ([1-(2,6-dimethylaniline)-2-(2,6-bis(4,4'-dimethoxybenzhydryl)-4-trifluoromethylaniline)acenaphthene] nickel bromide, denoted as Ni6) shown in formula (I), wherein R 1 is methyl, R 2 Methyl, R 3 For hydrogen.

[0214] Ni6 was prepared according to the method of Example 8, except that an equal molar amount of L6 prepared in Example 7 was used to replace L1. Yield: 78%.

[0215] The structural confirmation data are as follows:

[0216] FT-IR(cm -1 ):2832(w),1957(w),1643(w,v C＝N),1607(w),1583(w),1508(m),1461(w),1438(m),1382(w),1335(w),1300(m),1243(s) ,1174(m),1150(m),1032(s),956(w),874(w),829(w),771(w),736(w),700(w),660(w).

[0217] 19 F NMR (470 MHz, CDCl3): δ-57.17.

[0218] Elemental analysis: C 57 H 47 N2 (1115.51) theoretical value: C, 61.37; H, 4.25; N, 2.51. Exp. value: C, 61.17H, 4.29; N, 2.43.

[0219] Embodiment 14:

[0220] 1 μmol of the complex Ni4 (main catalyst) prepared in Example 11 and the co-catalyst MMAO were used to jointly catalyze ethylene polymerization under high pressure (10 atm):

[0221] a) The ethylene polymerization process was carried out in a 250 mL stainless steel autoclave equipped with a pressure control system, a temperature controller and a mechanical stirrer. The autoclave was evacuated and backfilled with nitrogen three times and then backfilled with ethylene once. When the reactor reached 30°C, toluene (25 mL) and a solution of Ni4 (1 μmol) dissolved in toluene (25 mL) were added in sequence. Then 1.22 mL of a cocatalyst MMAO (2.45 mol / L, n-heptane solution) and toluene (50 mL) were added, and the Al:Ni molar ratio was about 3000. Then ethylene was continuously introduced, and the speed was maintained at 400 revolutions per minute under the condition of maintaining the ethylene pressure at P(C2H4)=10 atm, and the mixture was stirred for 30 min and 30°C. After the reaction was completed, the ethylene supply was stopped, and the reactor was vented after cooling. The obtained mixture was quenched with a 15% by mass ethanol solution of hydrochloric acid, and the polymer was collected by filtration. After vacuum drying at 50°C for 8 hours, the polymer was weighed.

[0222] The polymerization activity was 10.16×10 6 g·mol -1 (Ni)·h -1 , T m =121.7℃,X c =43.7%, Mw=13.41×10 5 g·mol -1 , PDI=2.27.

[0223] Take 50 mg of the polymer obtained in Example 14a) and dissolve it in 5 mL of deuterated o-dichlorobenzene. Test the polymer at 100°C. 13 The signal was accumulated 2048 times, and the peak shift was between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, proving that the obtained polymer was branched polyethylene with a branching degree of 16 / 1000Cs (see NMR test spectrum for details). Figure 3 ).

[0224] b) is basically the same as Example 14a), except that 0.61 mL of the co-catalyst MMAO is added, and the Al:Ni molar ratio is about 1500.

[0225] The polymerization activity was 3.24×10 6 g·mol -1 (Ni)·h -1 , T m =113.8℃,X c =30.3%, Mw = 9.94 × 10 5 g·mol -1 , PDI=2.36.

[0226] c) is basically the same as Example 14a), except that 1.02 mL of co-catalyst MMAO is added, and the Al:Ni molar ratio is about 2500.

[0227] The polymerization activity was 8.24×10 6 g·mol -1 (Ni)·h -1 , T m =117.5℃,X c =38.3%, Mw=9.19×10 5 g·mol -1 , PDI=2.36.

[0228] d) is basically the same as Example 14a) except that 1.43 mL of co-catalyst MMAO is added, and the Al:Ni molar ratio is about 3500.

[0229] The polymerization activity was 7.14×10 6 g·mol -1 (Ni)·h -1 , T m =120.6℃,X c =43.1%, Mw=9.67×10 5 g·mol -1 , PDI=20.43.

[0230] e) is basically the same as Example 14a), except that the polymerization temperature is 20°C.

[0231] The polymerization activity was 6.52×10 6 g·mol -1 (Ni)·h -1 , polymer T m =120.8℃,X c =44.3%, Mw=16.84×10 5 g·mol -1 , PDI=2.07.

[0232] f) is basically the same as Example 14a), except that the polymerization temperature is 40°C.

[0233] The polymerization activity was 6.48×10 6 g·mol -1 (Ni)·h -1 , T m =112.7℃,X c =35.7%, Mw=6.41×10 5 g·mol -1 , PDI=2.03.

[0234] g) is basically the same as Example 14a), except that the polymerization temperature is 50°C.

[0235] The polymerization activity was 4.86×10 6 g·mol -1 (Ni)·h -1 , T m =111.9℃,X c =31.2%, Mw=6.70×10 5 g·mol -1 , PDI=1.94.

[0236] h) is basically the same as Example 14a), except that the polymerization temperature is 60°C.

[0237] The polymerization activity was 3.64×10 6 g·mol -1 (Ni)·h -1 , T m =117.4℃,X c =35.0%, Mw=6.66×10 5 g·mol -1 , PDI=2.77.

[0238] i) is basically the same as Example 14a), except that the polymerization temperature is 80°C.

[0239] The polymerization activity was 3.14×10 6 g·mol -1 (Ni)·h -1 , T m =117.7℃,X c =30.9%, Mw=4.57×10 5 g·mol -1 , PDI=8.74.

[0240] j) is basically the same as Example 14a), except that the polymerization time is 5 min.

[0241] The polymerization activity was 20.16×10 6 g·mol -1 (Ni)·h -1 , T m =117.4℃,X c =38.5%, Mw=7.84×10 5 g·mol -1 , PDI=2.13.

[0242] k) is basically the same as Example 14a), except that the polymerization time is 15 min.

[0243] The polymerization activity was 12.64×10 6 g·mol -1 (Ni)·h -1 , T m =118.5℃,X c =44.7%, Mw=8.65×10 5 g·mol -1 , PDI=2.71.

[0244] l) is basically the same as Example 14a), except that the polymerization time is 45 min.

[0245] The polymerization activity was 7.16×10 6 g·mol -1 (Ni)·h -1 , T m =122.7℃,X c =39.5%, Mw = 13.71 × 10 5 g·mol -1 , PDI=2.09.

[0246] m) is basically the same as Example 14a), except that the polymerization time is 60 min.

[0247] The polymerization activity was 6.03×10 6g·mol -1 (Ni)·h -1 , T m =122.9℃,X c =47.0%, Mw=14.07×10 5 g·mol -1 , PDI=2.41.

[0248] Embodiment 15:

[0249] Use Ni1 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (10atm):

[0250] The same as Example 14a), except that Ni1 was used as the main catalyst. The polymerization activity was 10.94×10 6 g·mol -1 (Ni)·h -1 , T m =111.3℃,X c =69.4%, Mw=2.73×10 5 g·mol -1 , PDI=7.89.

[0251] Embodiment 16:

[0252] Use Ni2 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (10atm):

[0253] The same as Example 14a), except that Ni2 was used as the main catalyst. The polymerization activity was 6.32×10 6 g·mol -1 (Ni)·h -1 , polymer T m =117.3℃,X c =37.3%, Mw = 14.06 × 10 5 g·mol -1 , PDI=2.57.

[0254] Embodiment 17:

[0255] Use Ni3 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (10atm):

[0256] The same as Example 14a), except that Ni4 was used as the main catalyst. The polymerization activity was 4.96×10 6 g·mol -1 (Ni)·h -1 , T m =113.3℃,X c =33.8%, Mw = 14.24 × 105 g·mol -1 , PDI=2.46.

[0257] Embodiment 18:

[0258] Use Ni5 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (10atm):

[0259] Basically the same as Example 14a), except that Ni5 is used as the main catalyst. Polymerization activity: 5.46×10 6 g·mol -1 (Ni)·h -1 , polymer T m =117.1℃,X c =37.3%, Mw = 13.72 × 10 5 g·mol -1 , PDI=2.31.

[0260] Embodiment 19:

[0261] Use Ni6 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (10atm):

[0262] The same as Example 14a), except that Ni6 was used as the main catalyst. The polymerization activity was 7.96×10 6 g·mol -1 (Ni)·h -1 , T m =108.3℃,X c =39.6%, Mw = 12.16 × 10 5 g·mol -1 , PDI=1.99.

[0263] Embodiment 20:

[0264] Use Ni4 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (5atm):

[0265] Basically the same as Example 14a). The difference is that the ethylene polymerization pressure is 5 atm. The polymerization activity is 6.34×10 6 g·mol -1 (Ni)·h -1 , T m =116.4℃,X c =30.9%, Mw = 8.99 × 10 5 g·mol -1 , PDI=2.10.

[0266] Embodiment 21:

[0267] Use Ni4 and co-catalyst MMAO to jointly catalyze ethylene polymerization under high pressure (1atm):

[0268] Basically the same as Example 14a). The difference is that the ethylene polymerization pressure is 1 atm. The polymerization activity is 1.52×10 6 g·mol -1 (Ni)·h -1 , T m =113.4℃,X c =28.9%, Mw=6.95×10 5 g·mol -1 , PDI=2.51.

[0269] Embodiment 22:

[0270] 1 μmol of complex Ni4 and cocatalyst Et2AlCl(DEAC) were used to catalyze ethylene polymerization under high pressure (10 atm):

[0271] a) The ethylene polymerization process was carried out in a 250 mL stainless steel autoclave equipped with a pressure control system, a temperature controller and a mechanical stirrer. The autoclave was evacuated and backfilled with nitrogen three times and then backfilled with ethylene once. When the reactor reached 30°C, toluene (25 mL) and a solution of Ni4 (1 μmol) dissolved in toluene (25 mL) were added in sequence. Then 1.2 mL of the cocatalyst Et2AlCl (0.5 mol / L, toluene solution) and toluene (50 mL) were added, and the Al:Ni molar ratio was about 600. Then ethylene was continuously introduced, and the speed was maintained at 400 revolutions per minute under the condition of maintaining the ethylene pressure at P(C2H4)=10 atm, and the mixture was stirred for 30 min of polymerization time and 30°C of polymerization temperature. After the reaction was completed, the ethylene supply was stopped, and the reactor was vented after cooling. The obtained mixture was quenched with 15% hydrochloric acid ethanol solution, filtered and the polymer was collected. After vacuum drying at 50°C for 8 hours, the polymer was weighed.

[0272] The polymerization activity was 19.87×10 6 g·mol -1 (Ni)·h -1 , T m =77.8,118.5℃,X c =1.3%, 4.7%, Mw=7.46×10 5 g·mol -1 , PDI=14.77.

[0273] Take 50 mg of the polymer obtained in Example 22a) and dissolve it in 5 mL of deuterated o-dichlorobenzene. Test the polymer at 100°C. 13The signal was accumulated 2048 times, and the signal peak shift was between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, proving that the obtained polymer was branched polyethylene with a branching degree of 101 / 1000Cs (see NMR test spectrum for details Figure 4 ).

[0274] The polyethylene obtained in Example 22a) was subjected to mechanical tensile property test, and the average value of five tests was obtained. The tensile strength was 11.1 MPa and the elongation at break was 700%. The stress-strain recovery test of the obtained polymer was performed, and the elastic recovery rate was 67.6% (see the mechanical property test spectrum for details). Figure 7 ,as well as Figure 8 The corresponding curve in Figure a).

[0275] b) is basically the same as Example 22a), except that 1.0 mL of co-catalyst Et2AlCl is added, and the Al / Ni molar ratio is 500:1.

[0276] The polymerization activity was 15.38×10 6 g·mol -1 (Ni)·h -1 , polymer T m =58.3,119.0℃,X c =7.8%,1.4%, Mw=5.63×10 5 g·mol -1 , PDI=6.14.

[0277] c) is basically the same as Example 22a), except that 1.4 mL of the co-catalyst Et2AlCl is added, and the Al / Ni molar ratio is 700:1.

[0278] The polymerization activity was 13.14×10 6 g·mol -1 (Ni)·h -1 , T m =59.6,113.5℃,X c =8.6%, 1.1%, Mw=6.77×10 5 g·mol -1 , PDI=17.84.

[0279] d) is basically the same as Example 22a), except that the polymerization temperature is 20°C.

[0280] The polymerization activity was 14.14×10 6 g·mol -1 (Ni)·h -1 , T m =50.3,119.6℃,Xc =8.2%,1.9%, Mw=13.62×10 5 g·mol -1 , PDI=7.25.

[0281] e) is basically the same as Example 22a), except that the polymerization temperature is 40°C.

[0282] The polymerization activity was 16.94×10 6 g·mol -1 (Ni)·h -1 , T m =45.7,118.2℃,X c =3.8%, 2.4%, Mw=5.80×10 5 g·mol -1 , PDI=8.68.

[0283] f) is basically the same as Example 22a), except that the polymerization temperature is 50°C.

[0284] The polymerization activity was 13.94×10 6 g·mol -1 (Ni)·h -1 , T m =42.7,120.1℃,X c =2.8%,5.7%, Mw=5.13×10 5 g·mol -1 , PDI=11.59.

[0285] The obtained polyethylene was subjected to mechanical tensile property test, and the average value was obtained after five tests. The tensile strength was 10.6MPa and the elongation at break was 689%. The obtained polymer was subjected to stress-strain recovery test, and the elastic recovery rate was 58.6% (see the mechanical property test spectrum for details). Figure 7 ,as well as Figure 8 The corresponding curve in graph b).

[0286] g) is basically the same as Example 22a), except that the polymerization temperature is 60°C.

[0287] The polymerization activity was 11.56×10 6 g·mol -1 (Ni)·h -1 , T m =29.4,117.4℃,X c =4.5%, 2.4%, Mw=4.02×10 5 g·mol -1 , PDI=5.29.

[0288] h) is basically the same as Example 22a), except that the polymerization temperature is 80°C.

[0289] The polymerization activity was 8.74×10 6 g·mol -1 (Ni)·h -1 , T m =116.8℃,X c =6.7%, Mw=3.64×10 5 g·mol -1 , PDI=9.05.

[0290] The obtained polyethylene was subjected to mechanical tensile property test, and the average value was obtained after five tests. The tensile strength was 4.8MPa and the elongation at break was 926%. The obtained polymer was subjected to stress-strain recovery test, and the elastic recovery rate was 41.2% (see the mechanical property test spectrum for details). Figure 7 ,as well as Figure 8 The corresponding curve in graph c).

[0291] i) is basically the same as Example 22a), except that the polymerization time is 5 min.

[0292] Polymerization activity: 33.48×10 6 g·mol -1 (Ni)·h -1 , T m =63.8,111.0℃,X c =9.6%, 0.5%, Mw=5.14×10 5 g·mol -1 , PDI=2.37.

[0293] j) is basically the same as Example 22a), except that the polymerization time is 15 min.

[0294] Polymerization activity: 27.28×10 6 g·mol -1 (Ni)·h -1 , polymer T m =60.9,113.4℃,X c =3.4%, 2.5%, Mw=5.99×10 5 g·mol -1 , PDI=5.16.

[0295] k) is basically the same as Example 22a), except that the polymerization time is 45 min.

[0296] The polymerization activity was 15.93×10 6 g·mol -1(Ni)·h -1 , T m =81.7,115.6℃,X c =3.3%,1.8%, Mw=8.25×10 5 g·mol -1 , PDI=10.54.

[0297] l) is basically the same as Example 22a), except that the polymerization time is 60 min.

[0298] The polymerization activity was 13.76×10 6 g·mol -1 (Ni)·h -1 , T m =89.6,113.1℃,X c =4.7%,0.6%, Mw=8.41×10 5 g·mol -1 , PDI=11.69.

[0299] Embodiment 23:

[0300] Use Ni1 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (10atm):

[0301] The same as Example 22a), except that Ni1 was used as the main catalyst. The polymerization activity was 11.04×10 6 g·mol -1 (Ni)·h -1 , T m =93.2,122.6℃,X c =4.7%,38%, Mw=9.35×10 5 g·mol -1 , PDI=3.66.

[0302] Take 50 mg of the polymer obtained in Example 23 and dissolve it in 5 mL of deuterated o-dichlorobenzene. Test the polymer at 100°C. 13 C data. The signal was accumulated 2048 times, and the signal peak shift was between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, proving that the obtained polymer is branched polyethylene with a branching degree of 51 / 1000Cs. (See NMR test spectrum for details Figure 5 ).

[0303] Embodiment 24:

[0304] Use Ni2 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (10atm):

[0305] The same as Example 22a), except that Ni2 was used as the main catalyst. The polymerization activity was 10.36×10 6 g·mol -1 (Ni)·h -1 , T m =86.3,113.2℃,X c =2.6%, 1.3%, Mw=9.24×10 5 g·mol -1 , PDI=7.28.

[0306] Embodiment 25:

[0307] Use Ni3 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (10atm):

[0308] The same as Example 22a), except that Ni3 was used as the main catalyst. The polymerization activity was 8.54×10 6 g·mol -1 (Ni)·h -1 , T m =59.5,111.4℃,X c =5.5%,0.8%, Mw=13.22×10 5 g·mol -1 , PDI=7.71.

[0309] Embodiment 26:

[0310] Use Ni5 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (10atm):

[0311] The same as Example 22a), except that Ni3 was used as the main catalyst. The polymerization activity was 15.22×10 6 g·mol -1 (Ni)·h -1 , T m =48.9,114.5℃,X c =6.2%,1.9%, Mw=8.32×10 5 g·mol -1 , PDI=7.13.

[0312] The polyethylene obtained in Example 26 was tested for mechanical tensile properties. Five tests were performed to obtain the average value. The tensile strength was 20.3 MPa and the elongation at break was 892%. The obtained polymer was tested for stress-strain recovery. The elastic recovery rate was 59.2% (see the mechanical properties test spectrum for details). Figure 7 ,as well as Figure 8The corresponding curve in graph d).

[0313] Embodiment 27:

[0314] Use Ni6 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (10atm):

[0315] The same as Example 22a), except that Ni6 was used as the main catalyst. The polymerization activity was 9.24×10 6 g·mol -1 (Ni)·h -1 , T m =117.0℃,X c =36.1%, Mw=9.70×10 5 g·mol -1 , PDI=2.13.

[0316] Take 50 mg of the polymer obtained in Example 27 and dissolve it in 5 mL of deuterated o-dichlorobenzene. Test the polymer at 100 °C. 13 C data. The signal was accumulated 2048 times, and the signal peak shift was between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, proving that the obtained polymer is branched polyethylene. The branching degree is 28 / 1000Cs (see NMR test spectrum for details Figure 6 ).

[0317] Embodiment 28:

[0318] Use Ni4 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (5atm):

[0319] The same as Example 22a), except that the ethylene polymerization pressure was 5 atm. The polymerization activity was 6.34×10 6 g·mol -1 (Ni)·h -1 , T m =59.9,110.5℃,X c =13.9%,0.6%, Mw=6.07×10 5 g·mol -1 , PDI=9.66.

[0320] Embodiment 29:

[0321] Use Ni4 and cocatalyst Et2AlCl (DEAC) to catalyze ethylene polymerization under high pressure (1atm):

[0322] The same as Example 22a), except that the ethylene polymerization pressure was 1 atm. The polymerization activity was 2.58×106 g·mol -1 (Ni)·h -1 , T m =117.2℃,X c =21.0%, Mw=5.74×10 5 g·mol -1 , PDI=9.0.

[0323] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. An acenaphthene-based α-diimine nickel complex, characterized in that: The acenaphthene-based α-diimine nickel complex has a structure shown in the following structural formula (I): Among them, R 1 , R 2 , R 3 are the same or different and are independently selected from hydrogen, methyl, ethyl or isopropyl; Each X is the same or different and is independently selected from F, Cl, Br or I; Φ represents 2. The acenaphthene-based α-diimine nickel complex according to claim 1, characterized in that: The acenaphthene-based α-diimine nickel complex has a structure shown in the following structural formula (I-1), (I-2), (I-3), (I-4), (I-5) or (I-6):

3. An intermediate of an acenaphthene-based α-diimine nickel complex, characterized in that: The intermediate has a structure shown in the following structural formula (II): Among them, R 1 , R 2 , R 3 and Φ have the definitions as described in claim 1.

4. The intermediate of the acenaphthene-α-diimine nickel complex according to claim 3, characterized in that: The intermediate has a structure shown in the following structural formula (II-1), (II-2), (II-3), (II-4), (II-5) or (II-6):

5. An acenaphthene imide compound, characterized in that: The acenaphthene imide compound has a structure shown in the following structural formula (III): Among them, Φ represents 6. An aniline compound, characterized in that The aniline compound has a structure shown in the following structural formula (IV): Among them, Φ represents 7. The method for preparing the acenaphthenyl α-diimine nickel complex having the structural formula (I) according to claim 1, characterized in that: The preparation method comprises: reacting the intermediate of structural formula (II) described in claim 3 or 4 with a nickel-containing compound to obtain the acenaphthene-based α-diimine nickel complex of structural formula (I) described in claim 1.

8. The preparation method according to claim 7, characterized in that: The nickel-containing compound is selected from nickel-containing halides; And / or, the reaction is carried out under anaerobic conditions; and / or, the molar ratio of the nickel-containing compound to the intermediate of the structural formula (II) is 2:(2-3); And / or, the reaction temperature is 0-35°C; the reaction time is 8-16 hours; And / or, the reaction is carried out in an organic solvent, and the organic solvent is selected from one or more cyclic ether solvents; And / or, the method further comprises the step of purifying the reaction product.

9. The preparation method according to claim 8, characterized in that: The molar ratio of the nickel-containing compound to the intermediate of the structural formula (II) is 2:(2-2.5); And / or, the reaction temperature is 10-30°C; And / or, the organic solvent is tetrahydrofuran; And / or, the purification includes the following operations: removing the solvent from the reaction product, then dissolving it in an organic solvent to precipitate, washing the obtained solid phase with anhydrous ether after solid-liquid separation, and then drying; the organic solvent is anhydrous ether.

10. The preparation method according to claim 9, characterized in that: The molar ratio of the nickel-containing compound to the intermediate of the structural formula (II) is 2:2.1; And / or, the reaction temperature is 20-25° C.; the reaction time is 12-16 hours.

11. The method for preparing the intermediate having structural formula (II) according to claim 3 or 4, characterized in that: The preparation method comprises: 1) stirring the acenaphthene imide compound of structural formula (III) as claimed in claim 5, a water-soluble zinc salt and a substituted aniline compound of structural formula (V) in the presence of an organic acid to obtain an intermediate product; Where R 1 , R 2 , R 3 Having the definition as claimed in claim 1; 2) adding the intermediate product into an organic solvent and adding a 2+ Combine the aqueous solution of the weak salt of the complex, stir the reaction, separate the organic layer, and obtain the intermediate of the structural formula (II); the weak salt of the complex is one or more of carbonate, bicarbonate, and oxalate.

12. The preparation method according to claim 11, characterized in that: In step 1), the organic acid is a carboxylic acid; And / or, in step 1), the molar volume ratio of the acenaphthene imide compound of structural formula (III) to the organic acid is 2 mmol:(1-7) mL; And / or, in step 1), the molar ratio of the acenaphthene imide compound of structural formula (III) to the substituted aniline compound of structural formula (V) is 2:(2-6); And / or, in step 1), the molar ratio of the imine acenaphthene compound of structural formula (III) to the water-soluble zinc salt is 2:(2-4); And / or, in step 1), the reaction is carried out under heating reflux, the reaction temperature is 60-150° C., and the reaction time is 2-6 h; And / or, in step 2), the 2+ The molar ratio of the weak acid ions in the weak acid salt aqueous solution combining to form the complex to the water-soluble zinc salt is (2.2-4.5):2.2; wherein the weak acid ions are carbonate ions, bicarbonate ions and / or oxalate ions; And / or, in step 2), the organic solvent is selected from one or more halogenated alkane solvents; And / or, in step 2), the reaction temperature is 15-30°C and the reaction time is 1-3h; And / or, it also includes the step of purifying the reaction product obtained in step 2), wherein the purification includes the following operations: removing the solvent in the reaction product obtained in step 2), dissolving it in dichloromethane, adding an alkane organic solvent for recrystallization, performing solid-liquid separation, and drying the obtained solid phase.

13. The preparation method according to claim 12, characterized in that: In step 1), the organic acid is selected from one or more of formic acid, acetic acid, oxalic acid or succinic acid; And / or, in step 1), the molar volume ratio of the acenaphthene imide compound of structural formula (III) to the organic acid is 2 mmol: (2-5) mL; And / or, in step 1), the molar ratio of the acenaphthene imide compound of structural formula (III) to the substituted aniline compound of structural formula (V) is 2:(2-4); And / or, in step 1), the molar ratio of the imine acenaphthene compound of structural formula (III) to the water-soluble zinc salt is 2:(2-3); And / or, in step 1), the reaction temperature is 105-135°C and the reaction time is 4-5h; And / or, in step 2), the 2+ The molar ratio of the weak acid ions in the weak acid salt aqueous solution combining to form the complex to the water-soluble zinc salt is (3.2-4.5):2.2; And / or, in step 2), the weak acid salt is selected from one or more of potassium carbonate, potassium bicarbonate, and potassium oxalate; And / or, in step 2), the organic solvent is one or more of methyl chloride, dichloromethane, dichloroethane, and chloroform; And / or, in step 2), the reaction temperature is 20-25°C and the reaction time is 1-1.5h; And / or, the alkane organic solvent in the purification is n-hexane.

14. The preparation method according to claim 13, characterized in that: In step 1), the molar volume ratio of the acenaphthene imide compound of structural formula (III) to the organic acid is 2 mmol:3 mL; And / or, in step 1), the molar ratio of the acenaphthene imide compound of structural formula (III) to the substituted aniline compound of structural formula (V) is 2:(2-3); And / or, in step 1), the molar ratio of the acenaphthene imide compound of structural formula (III) to the water-soluble zinc salt is 2:(2-2.5).

15. The method for preparing the acenaphthene imide compound having the structural formula (III) according to claim 5, characterized in that: The preparation method comprises: reacting the aniline compound of structural formula (IV) as claimed in claim 6 with acenaphthene-1,2-dione under the catalysis of an organic acid to obtain the imine acenaphthene ketone compound of structural formula (III).

16. The preparation method according to claim 15, characterized in that: The reaction is carried out in the presence of an organic solvent, wherein the organic solvent is selected from one or more of methanol, ethanol and toluene; and / or, the organic acid is selected from one or more of formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid; and / or, the molar ratio of the acenaphthene-1,2-dione to the organic acid is 2:(1-4); and / or, the molar ratio of the acenaphthene-1,2-dione to the aniline compound of the structural formula (IV) is 2:(2-3); And / or, the reaction temperature of the reaction is 0-30°C and the reaction time is 12-36h; And / or, it also includes a step of purifying the reaction product; the purification operation includes: performing solid-liquid separation on the reaction product, dissolving the obtained solid phase in an organic solvent, then adding methanol for recrystallization, and drying the obtained solid phase after solid-liquid separation.

17. The preparation method according to claim 16, characterized in that: The molar ratio of the acenaphthene-1,2-dione to the organic acid is 2:(1-2); and / or, the molar ratio of the acenaphthene-1,2-dione to the aniline compound of the structural formula (IV) is 2:(2-2.5); And / or, the reaction temperature of the reaction is 20-25°C and the reaction time is 20-24h; And / or, the organic solvent in the purification is dichloromethane.

18. The preparation method according to claim 17, characterized in that: The molar ratio of the acenaphthene-1,2-dione to the organic acid is 2:(1-1.5); And / or, the molar ratio of the acenaphthene-1,2-dione to the aniline compound of the structural formula (IV) is 2:

2.

19. A catalyst, characterized in that The catalyst comprises a main catalyst and an optional co-catalyst; the main catalyst is selected from the acenaphthene-based α-diimine nickel complex of structural formula (I) described in claim 1 or 2.

20. The catalyst according to claim 19, characterized in that The co-catalyst is selected from one or more of aluminoxane, alkylaluminum and alkylaluminum chloride.

21. The catalyst according to claim 20, characterized in that The aluminoxane is selected from methylaluminoxane and / or triisobutylaluminum-modified methylaluminoxane; The alkylaluminum chloride is selected from one or more of diethylaluminum monochloride, triethylaluminum trichloride or ethylaluminum dichloride.

22. The catalyst according to claim 20 or 21, characterized in that The molar ratio of Al in the co-catalyst to Ni in the main catalyst is (300-3500):

1.

23. The catalyst according to claim 22, characterized in that When the co-catalyst is aluminoxane, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (1500-3500):

1.

24. The catalyst according to claim 23, characterized in that When the co-catalyst is aluminoxane, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 2900-3100:

1.

25. The catalyst according to claim 22, characterized in that When the co-catalyst is alkylaluminum chloride, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (300-700):

1.

26. The catalyst according to claim 22, characterized in that When the co-catalyst is alkylaluminum chloride, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 550-650:

1.

27. Use of the catalyst according to any one of claims 19 to 26 in olefin polymerization.

28. The use according to claim 27, wherein the olefin polymerization reaction is ethylene polymerization reaction.

29. A method for preparing polyethylene, characterized in that: The polyethylene is prepared by catalyzing the polymerization reaction of ethylene using the catalyst described in any one of claims 19 to 26.

30. The preparation method according to claim 29, characterized in that: The reaction temperature of the polymerization reaction is 20-80° C., the reaction time is 5-120 min, and the reaction pressure is 0.3-20 atm.

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