Nickel complexes containing polyhalogen substituted acenyl alpha-diimine and methods of making and using the same

Abstract

The present application provides a polyhalogen-substituted acenyl alpha-diimine nickel complex shown in formula (I) or formula (II) for catalyzing ethylene polymerization, which has the advantages of high catalytic activity, low cost and stable performance. In ethylene polymerization, after activation with Et2AlCl and MMAO, all the nickel complexes exhibit high activity for ethylene polymerization at a high temperature of 60℃, and the catalytic activity is as high as 1.75×10 7 g (PE) mol ‑1 (Ni)h ‑1 , producing medium branched polyethylene (31-96B / 1000Cs) with medium molecular weight and narrow molecular weight distribution, and the activity is as high as 7.00×10 6 g (PE) mol ‑1 (Ni)h ‑1 , indicating that the catalyst system has good thermal stability (the catalyst of the present application has the best catalytic activity at 60℃, while the best catalytic temperature of the catalysts in formula 2-1 and 3-1 is 30 and 20℃, respectively, indicating that the catalyst system of the present application has better heat resistance and production stability in industrial application) and longer service life.

Description

Technical Field

[0001] This invention belongs to the field of olefin catalytic polymerization technology, specifically relating to a nickel complex containing polyhalogen-substituted acenaphthene α-diimine, its preparation method, and its application. Background Technology

[0002] Polyolefins, as a major category of industrial materials, possess various microstructures and many outstanding properties, such as economy, wear resistance, chemical inertness, and ease of recycling and reprocessing. Among them, branched polyolefins with different types and numbers of branches exhibit unique flexibility, ductility, rheology, film-forming properties, and transparency, making them a research hotspot. Transition metal catalyst-catalyzed copolymerization of ethylene and α-olefins is a conventional method for synthesizing branched polyolefins. Although this copolymerization technology for synthesizing polyethylene elastomers has been used in industrial production, it is undeniable that the use of comonomers significantly increases production costs and complicates the polymerization process.

[0003] The post-transition α-diimine nickel complexes proposed by Brookhart in the 1990s provided another viable option for the synthesis of branched polyolefins, thus sparking great research interest in academia and industry. Among them, the acenaphthene α-diimine nickel complex (Equation 1) can effectively catalyze the polymerization of ethylene to form branched polyethylene without the addition of any expensive α-olefin comonomers. Chain isomerization mediated by a series of β-H elimination / reinsertion steps by active nickel species is widely considered the mechanism for the formation of different types of branches. Although the advent of α-diimine nickel complexes was a major revolution in the field of olefin polymerization catalysts, their poor thermal stability limited their further industrial applications. Over the past two decades, the electronic and steric properties of the ligands have been continuously tuned to improve the catalytic activity and thermal stability of the catalysts, and to improve the microstructure of the resulting polymers.

[0004] This strategy of improving catalyst structure has been extensively explored and has made significant progress.

[0005]

[0006] Our research group has been dedicated to the design and development of olefin polymerization catalysts and the exploration of catalytic processes. We have conducted extensive research and structural optimization work on N^N, N^N^N, and N^O type post-transition metal catalysts (Coord. Chem. Rev. 2017, 350, 68–83). For example, introducing bulky substituents, such as cycloalkanes, diphenylmethyl, and dibenzocycloheptanyl, at the ortho position of the N-aryl group locks the axial position of the nickel center, restricting the axial rotation of the NC bond at high temperatures, thereby improving the thermal stability of the nickel complex. Notably, the asymmetric structure of the nickel complex and the appropriate steric hindrance of the ortho substituents on the N-aryl group can provide effective space for the coordination and insertion of ethylene monomers, significantly improving catalytic activity.

[0007] Furthermore, both computational and experimental studies have shown that the presence of electron-withdrawing groups on the N-aryl unit can enhance the Lewis acidity of the nickel center and positively impact the activity of nickel-based catalysts. Therefore, halide substituents, including fluorides and chlorides, as classic electron-withdrawing groups, have been used in ligand framework design. When N-2,6-diphenylmethyl-4-fluorophenyl is set as an N-aryl group on one side, the asymmetric acenaphthene diimine nickel complex (Formula 2) (J. Polym. Sci. Part A: Polym. Chem., 2015, 53, 1369–1378) exhibits better catalytic performance compared to the structure-related para-methyl-substituted analog (Formula 3) (Organometallics, 2011, 30, 2418–2424).

[0008]

[0009] Although the above structural improvements have enhanced these acenaphthene-based α-diimine nickel complex catalysts, there are still difficulties in basic research and constraints on industrialization to achieve industrialization. Therefore, developing nickel catalysts with good thermal stability and high activity in the commonly used industrial polymerization solvent n-hexane, and preparing branched polyethylene elastomers with excellent mechanical properties, are urgent problems to be solved. Summary of the Invention

[0010] In view of this, the present invention provides a class of nickel complexes containing polyhalogen-substituted acenaphthene α-diimine, their preparation methods, and applications. The catalyst provided by the present invention exhibits high catalytic activity and good thermal stability in olefin polymerization, especially ethylene polymerization, and can generate branched polyethylene elastomers with narrow molecular weight distribution and excellent mechanical properties.

[0011] The technical solution of the present invention is as follows:

[0012] The following are polyhalogen-substituted acenaphthene α-diimine nickel complexes as shown in formula (I) or formula (II):

[0013]

[0014]

[0015] Among them, R 1 R 2 They may be the same or different, each independently selected from fluorine, chlorine, or bromine;

[0016] R 3 R 4 R 5 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 alkyl;

[0017] R 6 R 7 R 8 R 9 R 10 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 alkyl;

[0018] X may be the same or different, and each is independently selected from Cl, Br or I.

[0019] According to an embodiment of the present invention, R 1 R 2 Whether they are the same or different, they are each independently selected from fluorine or chlorine;

[0020] R 3 R 4 R 5 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 alkyl;

[0021] R 6 R 7 R 8 R 9 R 10 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 alkyl;

[0022] X may be the same or different, and each is independently selected from Cl, Br or I.

[0023] According to an embodiment of the present invention, R 1 Selected from Cl; R 2 Selected from F;R 3 R 4 R 5 R 9 R 10 Selected from H;

[0024] R 6 R 7 R 8 Whether the two are the same or different, they are selected independently from H and C. 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl; for example, R 8 Selected from H or C 1-6 Alkyl; R 6 R 7 Same or different, selected independently from C 1-6 alkyl;

[0025] X is the same, and is selected from Cl, Br, or I.

[0026] The inventors have discovered that by modifying different substitution sites of the N-aryl group, especially by introducing halogen atoms at the para or ortho position, a highly active nickel catalyst with better stability in olefin polymerization can be obtained, and branched polyethylene elastomers with excellent mechanical properties can also be successfully prepared.

[0027] In some embodiments of the present invention, the nickel complex containing polyhalogen-substituted acenaphthene α-diimine shown in formula (I) has the structure shown in formulas (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), (I-9), or (I-10):

[0028]

[0029]

[0030] As an example, the complex shown in formula (I) can be selected from complexes having the following group definitions:

[0031] Ni1:R 1 =Cl;R 2 =F;R 6 =Me;R 7 =Me;R 8 =H; X=Br;

[0032] Ni2:R 1 =Cl;R 2 =F;R6 =Et;R 7 =Et;R 8 =H;X=Br;

[0033] Ni3:R 1 =Cl;R 2 =F;R 6 =i-Pr;R 7 =i-Pr;R 8 =H;X=Br;

[0034] Ni4:R 1 =Cl;R 2 =F;R 6 =Me;R 7 =Me;R 8 =Me;X=Br;

[0035] Ni5:R 1 =Cl;R 2 =F;R 6 =Et;R 7 =Et;R 8 =Me;X=Br;

[0036] Ni6:R 1 =Cl;R 2 =F;R 6 =Me;R 7 =Me;R 8 =H;X=Cl;

[0037] Ni7:R 1 =Cl;R 2 =F;R 6 =Et;R 7 =Et;R 8 =H;X=Cl;

[0038] Ni8:R 1 =Cl;R 2 =F;R 6 =i-Pr;R 7 =i-Pr;R 8 =H;X=Cl;

[0039] Ni9:R 1 =Cl;R 2 =F;R 6 =Me;R 7 =Me;R 8 =Me;X=Cl;

[0040] Ni10:R 1 =Cl;R 2 =F;R6 =Et;R 7 =Et;R 8 =Me; X=Cl.

[0041] All other substituents are H.

[0042] In some embodiments of the present invention, the nickel complex containing polyhalogen-substituted acenaphthene α-diimine of formula (II) has the structure shown in formula (II-1) or formula (II-2):

[0043]

[0044] As an example, the complex shown in formula (II) can be selected from complexes having the following group definitions:

[0045] Ni11:R 1 =Cl;R 2 =F; X=Br;

[0046] Ni12:R 1 =Cl;R 2 =F; X=Cl.

[0047] All other substituents are H.

[0048] The present invention also provides intermediate compounds represented by formula (III) or formula (IV):

[0049]

[0050] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 It has the definition described above.

[0051] In some embodiments of the present invention, the intermediate compound has the structure shown in formula (III-1), (III-2), (III-3), (III-4), (III-5), or (IV-1):

[0052]

[0053] As examples, the coordination intermediates shown in formulas (III) and (IV) are selected from coordination intermediates defined by the following groups:

[0054] L1:R 1=Cl;R 2 =F;R 6 =Me;R 7 =Me;R 8 =H;

[0055] L2:R 1 =Cl;R 2 =F;R 6 =Et;R 7 =Et;R 8 =H;

[0056] L3:R 1 =Cl;R 2 =F;R 6 =i-Pr;R 7 =i-Pr;R 8 =H;

[0057] L4:R 1 =Cl;R 2 =F;R 6 =Me;R 7 =Me;R 8 =Me;

[0058] L5:R 1 =Cl;R 2 =F;R 6 =Et;R 7 =Et;R 8 =Me;

[0059] L6:R 1 =Cl;R 2 =F.

[0060] The present invention also provides a method for preparing the intermediate compound represented by formula (III) or formula (IV), comprising the following steps:

[0061]

[0062] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 It has the definition described above;

[0063] 1) The acenaphthene shown in formula (V) is subjected to a substitution reaction with aniline shown in formula (VI) to obtain imine acenaphthene shown in formula (VII);

[0064] 2) The imine acenaphthene of formula (VII) obtained in step 1) is reacted with the compound of formula (VIII) and a water-soluble zinc salt in the presence of an organic acid to obtain intermediate compounds of formula (III) and formula (IV).

[0065] Preferably, in step 1), the substitution reaction can be carried out in a solution of dichloromethane and methanol under the catalysis of p-toluenesulfonic acid for 6-8 hours at room temperature, more preferably 6-7 hours.

[0066] Preferably, in step 1), the molar ratio of acenaphthene (V) to aniline (VI) can be 1 to 2:1, preferably 1.1:1.

[0067] Preferably, in step 2), the molar ratio of the iminoacenaphthene compound represented by formula (VII) to the organic acid is 1:(1-5); preferably, the molar ratio is 1:(1-2), more preferably 1:(1-1.2).

[0068] Preferably, in step 2), the molar ratio of the iminoacenaphthene compound represented by formula (VII) to the compound represented by formula (VIII) is 1:(1-5), more preferably 1:(1-2), and even more preferably 1:(1-1.2).

[0069] Preferably, in step 2), the reaction is carried out under reflux conditions, preferably at a reaction temperature of 60-150°C, more preferably at 60-100°C, and for a reaction time of 2-6 days, more preferably 2-3 days.

[0070] Preferably, in step 2), the organic solvent is one or more of dichloromethane, methanol, ethanol, isopropanol, or toluene, more preferably ethanol;

[0071] Preferably, in step 2), the organic acid is a carboxylic acid, preferably selected from one or more of formic acid, acetic acid, oxalic acid or succinic acid, and more preferably acetic acid;

[0072] Preferably, in step 2), the molar ratio of imine acenaphthene represented by formula (VII) to water-soluble zinc salt is 1:(1-5), more preferably 1:(1-2), and even more preferably 1:(1-1.2).

[0073] Preferably, the method further includes step 3), which includes adding the reaction product obtained in step 2) to an organic solvent, and adding a substance capable of reacting with Zn. 2+ A stable, bound aqueous solution of a weak acid salt is stirred to react and separate the organic layer.

[0074] Preferably, in step 3), the weak acid salt is one or more of carbonate, bicarbonate, and oxalate;

[0075] Preferably, in step 3), the ability to interact with Zn 2+ The molar ratio of the weak acid anion to the water-soluble zinc salt in the stable combined weak acid salt aqueous solution is (1-3):1, more preferably (2-3):1, and even more preferably 2:1; wherein the weak acid anion is carbonate ion, bicarbonate ion and / or oxalate ion, and when multiple of these ions are present, the molar amount of the weak acid anion in the aforementioned molar ratio is the total molar amount of each weak acid anion contained; preferably, the weak acid salt is selected from one or more of potassium carbonate, potassium bicarbonate and potassium oxalate.

[0076] Preferably, in step 3), the organic solvent is selected from one or more of haloalkane solvents, preferably one or more of chloromethane, dichloromethane, dichloroethane, and trichloromethane, and more preferably dichloromethane;

[0077] The present invention also provides a method for preparing the nickel complex containing polyhalogen-substituted acenaphthene α-diimine as shown in formula (I) or formula (II) as described above, comprising the following steps:

[0078] The intermediate compound shown in formula (III) or (IV) above is reacted with a nickel-containing compound (e.g., a complexation reaction) to obtain the nickel complex of formula (I) or (II) containing a polyhalogen-substituted acenaphthene α-diimide.

[0079] Preferably, the nickel-containing compound is selected from nickel-containing halides; for example, it can be one or more of (DME)NiBr2, NiCl2·6H2O, and NiBr2, more preferably (DME)NiBr2 or NiCl2·6H2O.

[0080] Preferably, the reaction is carried out under anaerobic conditions, specifically, for example, in a protective gas atmosphere, such as nitrogen or other gases that are inert to the reaction.

[0081] Preferably, the molar ratio of the nickel-containing compound and the intermediate compound shown in formula (III) or (IV) is 2:(2-3), more preferably 2:(2-2.5), and even more preferably 2:2.1.

[0082] Preferably, the reaction temperature is 0-35℃, more preferably 10-30℃, and even more preferably 20-25℃; the reaction time is preferably 8-16 hours, and even more preferably 12-16 hours.

[0083] Preferably, the reaction is carried out in an organic solvent selected from one or more alcohols and chloroalkane solvents, more preferably ethanol and dichloromethane.

[0084] Preferably, the method further includes a step of purifying the reaction product; more preferably, the purification includes the following operations: removing the solvent from the reaction product, for example by removing the solvent by vacuum pumping, then dissolving it in an organic solvent and precipitating the precipitate, and after solid-liquid separation, washing the obtained solid phase with anhydrous diethyl ether and then drying it; wherein the organic solvent is preferably anhydrous diethyl ether.

[0085] The present invention also provides a method for preparing the imine acenaphthene compound represented by formula (VII) above, the method comprising: reacting 2-diphenylmethyl-6-chloro-4-fluoroaniline, an aniline compound represented by formula (VI) above, and acenaphthene-1,2-dione represented by formula (V) under the catalysis of an organic acid to obtain the imine acenaphthene compound represented by formula (VII);

[0086] Preferably, the reaction is carried out in the presence of an organic solvent, which is selected from one or more of methanol, ethanol, and toluene, and more preferably methanol;

[0087] Preferably, the organic acid is selected from one or more of formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid, and more preferably p-toluenesulfonic acid;

[0088] Preferably, the molar ratio of the acenaphthene-1,2-dione to the organic acid is 5:(0.2-1), more preferably 5:(0.2-0.5), and even more preferably 5:(0.2-0.3);

[0089] Preferably, the molar ratio of the acenaphthene-1,2-dione and the aniline compound shown in formula (VI) is (2-3):2, more preferably (2-2.5):2, and even more preferably 2.1:2;

[0090] Preferably, the reaction temperature is 0-30℃, more preferably 20-25℃, and the reaction time is preferably 4-12h, more preferably 4-6h;

[0091] Preferably, the method further includes a step of purifying the reaction product; the purification operation includes: performing solid-liquid separation on the reaction product, for example, by filtration under normal pressure, dissolving the obtained solid phase in an organic solvent, then adding methanol for recrystallization to precipitate the solid phase, and drying the obtained solid phase after solid-liquid separation; preferably, the organic solvent is dichloromethane.

[0092] The present invention also provides a catalyst composition comprising a main catalyst and an optional co-catalyst; the main catalyst comprising one or more of the polyhalogen-substituted acenaphthene α-diimine nickel complexes as shown in formula (I) or formula (II) above;

[0093] 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), more preferably triisobutylaluminum-modified methylaluminoxane; the alkylaluminum chloride is selected from one or more of diethylaluminum chloride (Et2AlCl), triethylaluminum trichloride (EASC), or diethylaluminum dichlorochloride (EADC), more preferably diethylaluminum chloride;

[0094] Preferably, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (100-5000):1, for example (500-4000):1, such as (1000-3500):1;

[0095] More preferably, when the co-catalyst is an aluminoxane, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is (1000-4000):1, more preferably 2900-3100:1, for example 3000:1;

[0096] Preferably, when the co-catalyst is triisobutylaluminum modified methylaluminoxane (MMAO), the molar ratio of metal Al in the co-catalyst to the central metal Ni of the nickel complex shown in formula (I) is (1000-4000):1, more preferably (2000-3500):1, for example, 2000:1, 2500:1, 2750:1, 3000:1, 3500:1;

[0097] Preferably, when the co-catalyst is diethylaluminum chloride (Et2AlCl), the molar ratio of metallic Al in the co-catalyst to the central metallic Ni of the nickel complex shown in formula (I) is (100-1000):1, more preferably (300-700):1, for example, 300:1, 400:1, 500:1, 600:1, 700:1.

[0098] The present invention also provides the application of the catalyst composition described above in the catalytic polymerization reaction of olefins.

[0099] Preferably, the olefin polymerization reaction is an ethylene polymerization reaction.

[0100] The present invention further provides a method for preparing polyethylene, wherein the above-described catalyst composition is used to catalyze the polymerization reaction of ethylene to prepare the polyethylene;

[0101] Preferably, the polymerization temperature is 20–120°C, for example 20–70°C, such as 30°C, 40°C, or 50°C; the reaction pressure is preferably 0.3–30 atm, for example 5 atm or 10 atm.

[0102] The solvent used in the above polymerization reaction can be one or more of toluene, o-xylene, n-heptane, n-hexane, cyclopentane, cyclohexane, or methylcyclohexane.

[0103] The technical solution provided by this invention has the following beneficial effects:

[0104] 1. The preparation method of nickel complex containing polyhalogen-substituted acenaphthene α-diimine provided by the present invention has the advantages of mild reaction conditions, short reaction cycle and simple operation conditions.

[0105] 2. The polyhalogen-substituted acenaphthene α-diimine nickel complexes provided by this invention exhibit advantages such as high catalytic activity, low cost, and stable performance when used for catalytic ethylene polymerization. In ethylene polymerization, after activation with Et₂AlCl and MMAO, all nickel complexes show high activity for ethylene polymerization at a high temperature of 60°C, with catalytic activity reaching as high as 1.75 × 10⁻⁶. 7 g(PE)mol -1 (Ni)h -1 To produce medium molecular weight (M w 0.35-3.72×10 5 g mol -1 Medium-branched polyethylene (31-96 / 1000Cs) with a narrow molecular weight distribution (PDI: 1.62-2.62) still exhibited an activity as high as 7.00 × 10⁻⁶ after 45 minutes of polymerization. 6 g(PE)mol -1 (Ni)h -1 This indicates that the catalyst system has good thermal stability (the catalyst of this application has the best catalytic activity at 60℃, while the optimal catalytic temperatures of the catalysts in Formulas 2-1 and 3-1 are 30℃ and 20℃, respectively, indicating that the catalyst system of this application has better heat resistance and production stability in industrial applications) and a long service life.

[0106] 3. The polymers obtained by olefin polymerization catalyzed by the polyhalogen-substituted acenaphthene α-diimine nickel complex provided by this invention have high molecular weights and are macroscopically tunable. The molecular weight of polyethylene can be controlled by changing the ortho-substituents; the greater the steric hindrance of the ortho-substituents in this catalytic system, the higher the molecular weight. The molecular weight of polyethylene can also be controlled by changing the reaction conditions; in this catalytic system, the molecular weight gradually decreases with increasing temperature.

[0107] 4. The branching degree of the polymer obtained by olefin polymerization catalyzed by the polyhalogen-substituted acenaphthene α-diimine nickel complex provided by this invention is tunable. It exhibits high selectivity (up to 80%) for short-chain methyl branches. The branching degree has a wide tunable range, and the branching degree of the polymer obtained by the Ni / MMAO system is generally lower than that of Ni / Et2AlCl, with a branching degree range of (31-96) branches per 1000 carbon atoms.

[0108] 5. The polyhalogen-substituted acenaphthene-α-diimine nickel complexes provided in this invention can catalyze the polymerization of ethylene to produce polyethylene elastomers with excellent mechanical properties, showing great potential for industrial applications. The mechanical properties of polyethylene are related to its molecular weight; polyethylene with higher molecular weights exhibits better tensile strength. Therefore, Ni3 and Ni11 possess the best mechanical properties, with corresponding polyethylene elastic samples achieving a tensile strength of up to 25.3 MPa and an elongation at break of up to 1635%. Simultaneously, the polyethylene elastomers of this invention exhibit good elasticity, with an elastic recovery rate reaching approximately 60%.

[0109] 6. The nickel complex containing polyhalogen-substituted acenaphthene α-diimine provided by this invention can catalyze the polymerization of ethylene in n-hexane, a commonly used solvent in industrial production, and exhibits superior catalytic activity, indicating that the catalyst of this application has the potential for industrial conversion.

[0110] Terminology Definitions and Explanations

[0111] Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains.

[0112] The term "halogen" includes F, Cl, Br, or I.

[0113] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably "C". 1-6 Alkyl group. "C" 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, 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.

[0114] Term "C" 1-12 "Alkoxy" should be understood as -OC 1-12 Alkyl, wherein C 1-12 Alkyl groups have the above definition.

[0115] The term "halogenated C" 1-12 "alkyl" should be understood as C as above. 1-12A group formed by replacing 1, 2, 3, 4, 5, or 6 H in an alkyl group with a halogen, wherein C 1-12 Alkyl groups have the above definition. Attached Figure Description

[0116] Figure 1 This is a schematic diagram of the molecular structure of Ni1 obtained from a single crystal in Example 8 of the present invention.

[0117] Figure 2 This is a schematic diagram of the molecular structure of Ni10(H2O) obtained from a single crystal in Example 18 of the present invention.

[0118] Figure 3 The temperature-raised carbon NMR spectrum of polyethylene PE-60 / Ni1 obtained in toluene in Example 20h is shown.

[0119] Figure 4 The image shows the heated carbon NMR spectrum of polyethylene PE-60 / Ni3 obtained in toluene in Example 22.

[0120] Figure 5 The image shows the heated carbon NMR spectrum of polyethylene PE-60 / Ni11 obtained in toluene in Example 25.

[0121] Figure 6 This is the heated carbon NMR spectrum of polyethylene PE-55 / Ni1 obtained in toluene in Example 44.

[0122] Figure 7 This is the heated carbon NMR spectrum of polyethylene PE-55 / Ni3 obtained in toluene in Example 46.

[0123] Figure 8 The image shows the heated carbon NMR spectrum of polyethylene PE-55 / Ni11 obtained in toluene in Example 49.

[0124] Figure 9 The image shows the heated carbon NMR spectrum of polyethylene PE-55 / Ni11 obtained in n-hexane in Example 61.

[0125] Figure 10 The stress-strain curves are for the polyethylene samples obtained in Examples 22, 25, 49 and 61.

[0126] Figure 11 The graphs show the elastic recovery curves of the polyethylene samples obtained in Examples 49, 22 and 25. Detailed Implementation

[0127] To facilitate understanding of the present invention, the following description, in conjunction with embodiments, will further illustrate the invention. It should be understood that the following embodiments are merely for a better understanding of the invention and do not imply that the invention is limited to these embodiments.

[0128] In a preferred embodiment, the synthesis of the complex in the following examples is carried out according to the following reaction pathway:

[0129]

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

[0131] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

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

[0133] The molecular weights and molecular weight distributions of the polymers obtained in the following ethylene polymerization examples were determined using conventional high-temperature GPC methods. Melting points were determined using conventional DSC methods. Polymer activity was calculated using the following formula: Polymer activity = Polymer yield / (Catalyst dosage * Polymerization time). Branching degree was determined by dissolving 50 mg of the obtained polymer in 0.5 mL of deuterated o-dichlorobenzene at 110 °C. 13 The values ​​were calculated from C NMR data. Fracture strain and ultimate tensile stress were obtained by measuring the stress-strain curves of the sample strip at fracture at room temperature. Elastic recovery rate (SR) was obtained from DMA curve data measured at room temperature.

[0134] The structures of all the synthesized compounds described below were confirmed by nuclear magnetic resonance analysis and elemental analysis.

[0135] In Example 1, the specific method for preparing the aniline compound (2-diphenylmethyl-6-chloro-4-fluoroaniline) of structural formula (VI) is as follows: A 250 mL round-bottom flask contained benzyl alcohol (7.28 g, 50.00 mmol) and 2-chloro-4-fluoroaniline (9.22 g, 50.00 mmol). The mixture was stirred and heated to 120 °C, and then zinc chloride catalyst (4.08 g, 30.00 mmol) and hydrochloric acid (5 mL) were added to the reaction solution. The reaction 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 resulting residue was dissolved in dichloromethane (200 mL), washed with saturated aqueous ammonium chloride solution (3 × 70 mL), and then washed with saturated aqueous sodium chloride solution (3 × 70 mL). The organic phase was then dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to 10 mL. Then add 50 ml of methanol, use an ultrasonic-assisted recrystallization device to purify the residue, and obtain 11.60 g of white powder.

[0136] The structural verification data is as follows: 1H NMR (400MHz, CDCl3, TMS) δ7.15–7.26(m,6H,Ar–H p ,Ar–H m ), 7.04–6.99(m,4H,Ar–H o ),6.89(dd,J=7.9,2.9Hz,1H,Ar–H m ), 6.30–6.24(m, 1H, Ar–H m ),5.37(s,1H,CHPh2),3.74(s,2H,NH2).

[0137] 13 C NMR (101MHz, CDCl3, TMS) δ156.16,153.62,141.32,137.39,131.73,131.67,129.39,12 8.88,127.21,120.15,120.04,115.91,115.67,114.62,114.57,114.37,114.32,52.72.

[0138] FT-IR (cm) -1 ):3476(s),3385(s),3214(w),3060(m),3062(m),1633(s),1608(s),1510(s),1495(s),1449(s),1433(s),1340(s),1289(m),1253(w),12 30(s),1196(s),1172(s),1116(w),1094(m),1027(s),100(w),983(m) ),950(w),922(s),882(s),860(w),874(s),781(m),745(s),697(s).

[0139] Elemental analysis: C 19 H 15 Theoretical values ​​for ClFN (311.09): C, 73.19; H, 4.85; N, 4.49. Experimental values: C, 72.85; H, 4.77; N, 4.36.

[0140] Example 1

[0141] Prepare the imine acenaphthene compound (2-diphenylmethyl-6-chloro-4-fluorophenylimine) acenaphthene as shown in formula (VII).

[0142] In a 250 mL round-bottom flask, acenaphthene-1,2-dione (7.90 g, 38.50 mmol) and p-toluenesulfonic acid (1.44 g, 8.40 mmol) as shown in structural formula (V) were added and dissolved in a mixture of methanol (500 mL) and dichloromethane (125 mL). The solution was stirred continuously at room temperature for 1 hour. Then, a solution containing aniline compound (2-diphenylmethyl-6-chloro-4-fluoroaniline) (10.89 g, 35.0 mmol) was added dropwise to the mixture, and the mixture was stirred at room temperature for 6 hours. Finally, 5 mL of triethylamine was added dropwise to the mixture to terminate the reaction. After filtration and concentration, a crude product was obtained. The crude product was then dissolved in 3 mL of dichloromethane, and 50 mL of methanol was slowly added. Recrystallization was performed using an ultrasonic apparatus to purify the crude product. Solid-liquid separation yielded 10.71 g of orange powder. The structural confirmation data are as follows: 1 H NMR (400MHz, CDCl3, TMS) δ8.14 (d, J=8.7Hz, 1H, An–H), 7.96 (t, J=7.5Hz, 2H, An–H), 7.76–7.67 (m, 3H, An–H), 7.34–7.27 (m, 6H, Ar–H o ,Ar–H m ),7.11(m,4H,Ar–H p ), 6.99–6.96(m, 1H, Ar–H m ),6.35(dd,J=9.5,3.1Hz,1H,Ar–H m ),5.45(s,1H,CHPh2).

[0143] 13 C NMR (101MHz, CDCl3, TMS) δ198.18,156.55,154.18,141.50,137.44,135.10,132.33,132.20,132.13,131.12,130.45,129.68,1 29.17,128.62,128.50,127.50,126.64,122.44,121.65,120.60,120.50,116.24,116.00,114.91,114.65,99.98,77.36,51.64.

[0144] FT-IR (cm) -1):3068(m),3033(m),2989(w),2920(w),1724(s),1724(s),1651(s), 1581(s),1494(s),1454(s),1449(s),1473(s),1414(s),1348(w),131 8(w),1270(s),1245(m),1215(s),1178(m),1149(m),1108(w),1074(s) ),1027(s),948(s),910(s),870(s),829(s),773(s),742(s),696(s).

[0145] Elemental analysis: C 31 H 19 Theoretical values ​​for ClFNO(475.11): C, 78.23; H, 4.02; N, 2.94. Experimental values: C, 78.13; H, 4.02; N, 2.95.

[0146] Example 2

[0147] The intermediate 1-(2,6-dimethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene, which is used to prepare the acenaphthene-α-diimine nickel complex shown in formula (III), is denoted as ligand L1.

[0148] In a 100 mL round-bottom flask, 0.27 g of zinc chloride, 0.95 g (2.00 mmol) of compound (2-diphenylmethyl-6-chloro-4-fluorophenylimine) acenaphthene prepared in Example 1, 0.25 g (2.00 mmol) of 2,6-dimethylaniline, and 0.12 g (2.00 mmol) of acetic acid were added to 4 mL of ethanol. After thorough mixing, the mixture was refluxed at 80 °C and stirred for 3 days. Once cooled to room temperature, a yellow precipitate (a solid zinc chloride complex) was obtained. The yellow precipitate was filtered and washed with ether to obtain the zinc chloride (II) complex. A saturated aqueous solution of potassium carbonate (4.4 mmol of potassium carbonate and 6 mL of water) was added to a 100 mL solution of dichloromethane containing the zinc chloride (II) complex, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated by extraction. After removing volatiles by rotary evaporation, the separated organic layer was dissolved in 5 mL of dichloromethane, and 10 mL of methanol solution was slowly added. The product was then recrystallized at room temperature using an ultrasonic-assisted method to obtain ligand L1. After solid-liquid separation, the obtained solid phase was dried to obtain 0.58 g of orange powder.

[0149] The structural verification data is as follows: 11H NMR (400 MHz, CDCl3, TMS) δ 7.79 (t, J = 8.1 Hz, 2H, An–H), 7.33–7.27 (m, 3H, An–H), 7.26–7.17 (m, 4H, An–H, Ar–H), 7.16–7.07 (m, 4H, Ar–H), 6.98 (d, J = 7.1 Hz, 2H, Ar–H m ), 6.75 (dd, J = 9.4, 2.7 Hz, 1H, Ar-H m ), 6.61–6.50 (m, 4H, Ar–H), 6.29 (t, J = 7.4 Hz, 1H, Ar–H p ), 5.85 (s, 1H, CHPh2), 2.29 (s, 3H, CH3), 2.09 (s, 3H, CH3).

[0150] 13 13C NMR (101 MHz, CDCl3, TMS) δ 164.17, 161.10, 160.10, 157.71, 149.07, 143.24, 143.15, 141.90, 140.63, 140.43, 137.94, 130.38, 129.82, 129.52, 129.07, 129.01, 128.93, 128.83, 128.44, 128.20, 127.94, 127.69, 127.44, 126.72, 125.64, 124.83, 124.79, 123.86, 123.09, 122.74, 122.63, 122.16, 115.62, 115.39, 115.10, 114.84, 52.97, 18.18, 17.74.

[0151] FT-IR (cm -1 ): 3061 (m), 3042 (w), 3024 (w), 2962 (w), 2918 (w), 2849 (w), 1673 (ν C＝N , m), 1644 (ν C＝N , m), 1591 (s), 1577 (s), 1439 (m), 1436 (s), 1356 (w), 1330 (w), 1259 (S), 1231 (m), 1119 (m), 1081 (S), 1026 (m), 986 (s), 920 (s), 803 (w), 800 (m), 781 (s), 761 (s), 786 (s), 696 (s). Elemental analysis: C 39 H 28Theoretical values ​​for ClFN2 (579.12): C, 80.89; H, 4.87; N, 4.84. Experimental values: C, 80.51; H, 4.63; N, 4.93.

[0152] Example 3

[0153] The intermediate 1-(2,6-diethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene, which is used to prepare the acenaphthene-α-diimine nickel complex shown in formula (III), is denoted as ligand L2.

[0154] Ligand L2, 0.56 g, was prepared according to the method in Example 2, except that 2,6-dimethylaniline was replaced with an equimolar amount of 2,6-diethylaniline.

[0155] The structural verification data is as follows: 1 H NMR (400MHz, CDCl3, TMS) δ7.74 (dd, J=8.0, 6.6Hz, 2H, An–H), 7.26 (t, J=7.5Hz, 3H, An–H, Ar–H), 7.22–7.10 (m, 8H, An–H, Ar–H), 6.95 (d, J=7.2Hz, 2H, Ar–H m ),6.72(dd,J=9.4,2.7Hz,1H,Ar–H p ),6.56–6.47(m,4H,Ar–H),6.26(t,J=7.4Hz,1H,Ar–H),5.82(s,1H,CHPh2),2.74–2.64(m,1H,CH2CH3),2.60– 2.45(m,2H,CH2CH3),2.37–2.28(m,1H,CH2CH3),1.22(t,J=7.5Hz,3H,CH2CH3),1.02(t,J=7.5Hz,3H,CH2CH3).

[0156] 13C NMR (101MHz, CDCl3, TMS) δ163.40,159.91,159.02,156.66,146.93,142.10,140.69,139.5 0,139.29,136.94,136.53,129.69,129.63,129.30,128.74,128.47,128.02,127.87,127. 84,127.71,127.39,126.71,126.38,125.67,125.42,125.24,124.62,123.15,122.03,122.00,121.67,121.56,114.50,114.27,114.11,113.73,51.76,23.93,23.23,13.45,12.77.

[0157] FT-IR (cm) -1 ):3067(w),306(w),2962(s),2936(w),2876(w),2837(w),1667(ν C＝N ,m),1643(ν C＝N ,m),1592(m),1574(m),1494(m),1455(s),1435(s),1330(w),1358(w),1259(s),122 5(m),1193(m),1084(s),1017(s),925(m),921(m),861(m),797(s),738(s),693(s).

[0158] Elemental analysis: C 41 H 32 Theoretical values ​​for ClFN2 (607.17): C, 81.11; H, 5.31; N, 4.61. Experimental values: C, 81.36; H, 5.43; N, 4.82.

[0159] Example 4

[0160] The intermediate 1-(2,6-diisopropylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene, which is used to prepare the nickel acenaphthene α-diimine complex shown in formula (III), is denoted as ligand L3.

[0161] Ligand L3, 0.52 g, was prepared according to the method in Example 2, except that 2,6-dimethylaniline was replaced with an equimolar amount of 2,6-diisopropylaniline.

[0162] The structural verification data is as follows: 1H NMR(400MHz,CDCl3,TMS)δ7.76(dd,J=8.2,5.7Hz,2H,An–H),7.32–7.27(m,4H,An–H o ,An–H m ),7.25(d,J=4.7Hz,2H,Ar–H),7.24–7.12(m,5H,Ar–H),6.96(d,J=7.1Hz,2H,Ar–H m ),6.75(dd,J=9.4,2.7Hz,1H,Ar–H p ),6.55–6.47(m,4H,Ar–H),6.28(t,J=7.4Hz,1H,Ar–H),5.84(s,1H,CHPh2),3.24–3.19(m,1H,CH(CH3)2),2.98–2.87(m,1H,CH(CH3)2),1.33(d,J=6.8Hz,3H,CH(CH3)2),1.20(d,J=6.8Hz,3H,CH(CH3)2),1.13(d,J=6.9Hz,3H,CH(CH3)2),0.85(d,J=6.9Hz,3H,CH(CH3)2).

[0163] 13 C NMR(101MHz,CDCl3,TMS)δ164.34,161.41,160.08,157.69,147.04,143.35,141.97,140.58,140.48,137.99,137.92,135.57,135.47,130.36,129.80,129.54,129.09,128.85,128.81,128.78,128.45,127.78,127.52,127.37,126.73,125.70,124.56,123.72,123.33,123.07,122.75,122.65,115.58,115.29,115.14,114.94,52.79,28.63,28.50,23.74,23.61,23.47,23.13.

[0164] FT-IR(cm -1 ):3059(w),3024(w),2958(m),2922(w),2868(m),1678(ν C＝N ,m),1645(ν C＝N,m),1593(s),1492(m),1434(s),1380(w),1358(m),1326(m),1273(s),1247(m),1223(m),1194(s),1153( w),1105(m),1078(m),984(m),1039(s),924(s),884(m),854(s),826(m),806(m),772(s),741(s),698(s).

[0165] Elemental analysis: C 43 H 36 ClFN2 (635.22) theoretical values: C, 81.31; H, 5.71; N, 4.41. Experimental values: H, 5.37; N, 4.52. Example 5

[0166] The intermediate 1-(2,4,6-trimethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene, which is used to prepare the acenaphthene α-diimine nickel complex shown in formula (III), is denoted as ligand L4.

[0167] Ligand L4, 0.57 g, was prepared according to the method in Example 2, except that 2,6-dimethylaniline was replaced with an equimolar amount of 2,4,6-trimethylaniline.

[0168] The structural verification data is as follows: 1 H NMR(400MHz, CDCl3, TMS) δ7.78(t,J=8.3Hz,2H,An–H),7.33–7.21(m,5H,An–H,Ar–H),7.16(dd,J=8 .1,2.7Hz,1H,Ar–H),7.12(d,J=7.3Hz,2H,Ar–H),6.98(d,J=8.8Hz,2H,Ar–H),6.96(s,2H,Ar–H),6. 73(dd,J=9.4,2.7Hz,1H,Ar–H),6.65(d,J=6.9Hz,1H,Ar–H),6.52(dd,J=16.1,7.6Hz,3H,Ar–H),6. 27(t,J=7.4Hz,1H,Ar–H),5.83(s,1H,CHPh2),2.37(s,3H,CH3),2.23(s,3H,CH3),2.04(s,3H,CH3).

[0169] 13C NMR (101MHz, CDCl3, TMS) δ164.32,161.27,160.28,157.68,146.45,143.24,141.78,140 .58,140.36,138.01,137.94,133.08,130.35,129.85,129.84,129.06,129.02,128.73,1 28.45, 127.94, 127.69, 127.40, 126.71, 125.62, 124.60, 124.56, 123.07, 123.03, 122.74, 122.63, 122.21, 122.16, 115.69, 115.38, 115.06, 114.85, 52.85, 20.88, 18.11, 17.70.

[0170] FT-IR (cm) -1 ):3057(w),3023(w),3003(w),2962(m),2916(w),2856(w),2716(w),1673(ν C＝N ,m),1641(ν C＝N ,m),1593(s),1574(s),1494(m),1474(w),1434(s),1360(w),1331(m),1298(w),1260(s),1228(m)1193(m),1146(m), 1080(s),1023(s),984(s),949(m),917(m),882(s),861(w),838(s),833(w),824(w),802(m),782(s),738(s),695(s).

[0171] Elemental analysis: C 40 H 30 Theoretical values ​​for ClFN2 (593.14): C, 81.00; H, 5.10; N, 4.72. Experimental values: C, 80.64; H, 5.07; N, 4.41.

[0172] Example 6

[0173] The intermediate 1-(2,6-diethyl-4-methylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene, which is used to prepare the acenaphthene α-diimine nickel complex shown in formula (III), is denoted as ligand L5.

[0174] L5, 0.53 g, was prepared according to the method in Example 2, except that 2,6-dimethylaniline was replaced with an equimolar amount of 2,6-diethyl-4-methylaniline.

[0175] The structure confirmation data are as follows: 1 H NMR (400 MHz, CDCl3, TMS) δ 7.70 (t, J=8.0 Hz, 2H, An–H), 7.22 (dt, J=14.3, 7.1 Hz, 3H, An–H), 7.18–7.09 (m, 3H, An–H, Ar–H), 7.07 (d, J=7.3 Hz, 2H, Ar–H), 6.93 (dd, J=19.8, 11.4 Hz, 4H, Ar–H), 6.68 (dd, J=9.4, 2.7 Hz, 1H, Ar–H), 6.58 (d, J=7.1 Hz, 1H, Ar–H), 6.49–6.42 (m, 3H, Ar–H), 6.22 (t, J=7.4 Hz, 1H, Ar–H), 5.78 (s, 1H, CHPh2), 2.67–2.57 (m, 1H, CH2CH3), 2.53–2.37 (m, 2H, CH2CH3), 2.36 (s, 3H, CH3), 2.31–2.21 (m, 1H, CH2CH3), 1.17 (t, J=7.5 Hz, 3H, CH2CH3), 0.97 (t, J=7.5 Hz, 3H, CH2CH3).

[0176] 13 C NMR (101 MHz, CDCl3, TMS) δ 164.32, 161.32, 160.10, 157.67, 145.73, 143.34, 141.88, 140.55, 140.47, 138.00, 137.93, 133.30, 130.59, 130.53, 130.34, 129.79, 129.53, 129.02, 128.89, 128.64, 128.44, 127.75, 127.39, 127.28, 127.22, 127.09, 127.03, 126.70, 125.66, 123.03, 122.71, 122.63, 115.53, 115.30, 115.10, 114.84, 52.80, 24.81, 24.56, 21.20, 14.70, 13.86.

[0177] FT-IR (cm -1 ): 3110 (w), 3074 (m), 3056 (w), 3028 (m), 3005 (w), 2996 (w), 2958 (s), 2930 (w), 2914 (w), 2894 (w), 2860 (w), 2831 (w), 1664 (ν C＝N , m), 1641 (ν C＝N,m),1592(s),1574(m),1494(m),1457(s),1440(s),1420(s),1392(w),1379(w),1369(w),135 9(m),1337(w),1323(w),1274(s),1242(s),1224(m),1195(s),1181(m),1153(w),1142(m),10 93(m),1085(m),1077(m),1062(w),1044(m),1031(m),1003(w),991(m),948(m),931(m),919( w),913(m),890(s),881(s),860(s),835(s),821(m),799(s),786(s),776(s),739(s),698(s).

[0178] Elemental analysis: C 42 H 34 Theoretical values ​​for ClFN2 (621.20): C, 81.21; H, 5.52; N, 4.51. Experimental values: C, 81.59; H, 5.83; N, 4.74.

[0179] Example 7

[0180] The intermediate bis(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene, as shown in formula (IV), is designated as ligand L6.

[0181] In the process of synthesizing the imine acenaphthene compound (2-diphenylmethyl-6-chloro-4-fluorophenylimine) acenaphthene as shown in (VII), 1.87 g of yellow powder as a byproduct was obtained as L6.

[0182] The structural verification data is as follows: 1 H NMR (600MHz, CDCl3, TMS) δ7.68 (d, J=8.2Hz, 2H, An–H), 7.30–7.28 (m, 4H, An–H), 7 .26–7.22(m,4H,Ar–H),7.19–7.16(m,2H,Ar–H),7.13(d,J=7.5Hz,4H,Ar–H),6.93 (d,J=7.1Hz,4H,Ar-H),6.77(dd,J=9.4,2.7Hz,2H,Ar-H),6.42(d,J=7.2Hz,2H,Ar -H), 6.36 (t, J = 7.7Hz, 4H, Ar-H), 6.08 (t, J = 7.4Hz, 2H, Ar-H), 5.77 (s, 2H, CHPh2).

[0183] 13 C NMR (151MHz, CDCl3, TMS) δ164.83,159.00,143.13,141.70,140.37,140.00,138.04,129.91,129 .50,128.77,128.40,127.64,127.06,126.69,125.30,122.78,115.56,114.88,52.80.FT-IR(cm -1 ):3295(m),3189(w),3159(w),3070(s),3025(m),2963(w),2921(w),2866(w),162(ν C＝N ,s),1640(ν C＝N ,s),1594(s),1574(s),1494(s),1456(s),1448(w),1433(s),1360(w),1326(w),1299(w),1273(s),1246(m),1221(s),1 189(s)1158(m),1103(m),1080(s),1034(s),989(s),951(w),912(s),884(s),859(s),825(s),774(s),740(s),696(s).

[0184] Elemental analysis: C 50 H 32 Cl2F2N 2. Theoretical values ​​for CH3OH (801.76): C, 76.40; H, 4.53; N, 3.49. Experimental values: C, 76.52; H, 4.27; N, 3.56.

[0185] Example 8

[0186] The intermediate [1-(2,6-dimethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] nickel bromide, which is the preparation of the acenaphthene α-diimine nickel complex shown in formula (I), is denoted as complex Ni1.

[0187] At room temperature, (DME)NiBr2 (ethylene glycol dimethyl ether nickel bromide) (0.11 g, 0.35 mmol) and ligand L1 (0.20 g, 0.35 mmol) prepared in Example 2 were mixed and dissolved in a mixed solution of ethanol (6 mL) and dichloromethane (9 mL). The mixture was stirred for 12 h under nitrogen protection. After removing the solvent under reduced pressure, anhydrous diethyl ether (7 mL) and n-hexane (15 mL) were added to induce precipitation, from which a red solid was precipitated. The solid was filtered, washed with n-hexane, and dried to obtain 0.25 g of brown solid complex.

[0188] The structural verification data is as follows:

[0189] FT-IR (cm) -1 ):3577(m),3310(s),3087(w),3062(m),3026(w),2953(w),1913(w),2844(w),2739(w),1653(ν C＝N ,m),1624(ν C＝N ,m),1587(s),1494(w),1442(s),1354(m),1326(w),1289(s),1253(w),1234(m),1227(m),1186(s),1126(w),1 091(m),1050(m),1030(m),992(s),948(w),921(w),885(m),860(m),828(m),810(w),771(s),738(m),699(s).

[0190] Elemental analysis: C 39 H 28 Theoretical values ​​for Br₂ClFN₂Ni (797.62): C, 58.73; H, 3.54; N, 3.51. Experimental values: C, 58.91; H, 3.60; N, 3.59.

[0191] A mixed solution of diethyl ether and hexane (v:v = 2:1) was diffused into a saturated dichloromethane solution of the complex using a slow diffusion method at room temperature, resulting in the growth of Ni1 single crystals suitable for X-ray diffraction. For clarity, all hydrogen atoms in the complex molecular structure were omitted from the ORTEP diagram; the perspective view of the crystal molecular structure is shown below. Figure 1 As shown, it has an asymmetric structure, and the coordinating atoms exhibit a distorted tetrahedral geometry around the nickel center.

[0192] Example 9

[0193] The intermediate [1-(2,6-diethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] nickel bromide, denoted as complex Ni2, is used to prepare the acenaphthene α-diimine nickel complex shown in formula (I).

[0194] Ni2 was prepared according to the method in Example 8, except that an equimolar amount of L2 prepared in Example 3 was used to replace L1. Yield: 83%.

[0195] The structural verification data is as follows:

[0196] FT-IR (cm) -1):3349(s),3076,3029(m),2967(m),2932(m),2877(w),2840(w),1650(ν C＝N ,m),1621(ν C＝N ,m),1597(s),1589(w),1581(s),1490(w),1472(w),1462(w),1453(m),1448(s) ,1438(m),1417(w),1350(w),1292(s),1289(s),1220(m),1189(m),1166(w),115 2(w),1127(m),1097(w),1083(m),1049(w),1028(s),989(m),955(w),921(w),88 9(w),867(s),850(w),828(s),820(w),810(m),791(w),772(s),742(s),701(s).

[0197] Elemental analysis: C 41 H 32 Theoretical values ​​for Br2ClFN2Ni (825.67): C, 59.64; H, 3.91; N, 3.39. Experimental values: C, 60.02; H, 4.01; N, 3.35.

[0198] Example 10

[0199] The intermediate [1-(2,6-diisopropylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] nickel bromide, which is used to prepare the acenaphthene α-diimine nickel complex shown in formula (I), is denoted as complex Ni3.

[0200] Ni3 was prepared according to the method in Example 8, except that L1 was replaced with an equimolar amount of L3 prepared in Example 4. Yield: 83%.

[0201] The structural verification data is as follows:

[0202] FT-IR (cm) -1 ):3539(w)3341(s),3076(w),3066(w),3029(m),2958(m),2923(w),2863(w),1646(ν C＝N ,m),1620(ν C＝N,m),1583(s),1493(m),1453(s),1450(m),1438(s),1380(w),1356(w),1325(w),1285(s),1273(m),1251(w),1223(m),1183(s),1153( w),1150(w),1095(s),1078(w),1049(w),1029(s),987(s),947(m),925(m),885(m),851(m),826(m),806(m),770(s),738(s),698(s).

[0203] Elemental analysis: C 43 H 36 Theoretical values ​​for Br2ClFN2Ni (853.72): C, 60.50; H, 4.25; N, 3.28. Experimental values: C, 60.72; H, 4.29; N, 3.35.

[0204] Example 11

[0205] The intermediate [1-(2,4,6-trimethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] nickel bromide, which is used to prepare the acenaphthene α-diimine nickel complex shown in formula (I), is denoted as complex Ni4.

[0206] Ni4 was prepared according to the method in Example 8, except that L1 was replaced with an equimolar amount of L4 prepared in Example 5. Yield: 87%.

[0207] The structural verification data is as follows:

[0208] FT-IR (cm) -1 ):3578(m),3338(s),3058(w),2914(w),2856(w),2806(w),2730(w),1654(ν C＝N ,m),1625(ν C＝N ,m),1586(s),1494(s),1490(m),1442(s),1418(w),1352(m),1289(s),1237(s),1233(w),1226(s),1187(s),1153(w),1125(w), 1103(w),1079(m),1050(m),1029(s),992(s),953(m)922(s),885(m),858(m),845(m),829(s),804(s),771(s),737(s),699(s).

[0209] Elemental analysis: C40 H 30 Theoretical values ​​for Br₂ClFN₂Ni(811.64): C, 59.19; H, 3.73; N, 3.45. Experimental values: C, 59.17; H, 3.82; N, 3.33.

[0210] Example 12

[0211] The intermediate [1-(2,6-diethyl-4-methylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] nickel bromide, which is used to prepare the acenaphthene α-diimine nickel complex shown in formula (I), is denoted as complex Ni5.

[0212] Ni5 was prepared according to the method in Example 8, except that an equimolar amount of L5 prepared in Example 6 was used to replace L1. Yield: 82%.

[0213] The structural verification data is as follows:

[0214] FT-IR (cm) -1 ):35 76(m),3542(m),3333(w),3083(w),3062(w),3026(w),2960(s),2927(w),2870(w),1648(ν C＝N ,m),1619(ν C＝N ,m),1585(s),1491(m),1451(s),1442(s),1416(m),1377(w),1350(w),1286(m),1228(m),1186(s),1150(w),1127(w),1082(m), 1099(m),1079(w),1051(w),1030(m),991(m),951(m),923(m),886(s),855(s),828(s),812(w),809(m),773(s),739(s),699(s).

[0215] Elemental analysis: C 42 H 34 Theoretical values ​​for Br2ClFN2Ni (839.70): C, 60.08; H, 4.08; N, 3.34. Experimental values: C, 60.21; H, 4.10; N, 3.29.

[0216] Example 13

[0217] The intermediate [bis(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] nickel bromide, which is the preparation of the acenaphthene α-diimine nickel complex shown in formula (II), is denoted as complex Ni11.

[0218] Ni11 was prepared according to the method in Example 8, except that an equimolar amount of L6 was used to replace L1. Yield: 81%.

[0219] The structural verification data is as follows:

[0220] FT-IR (cm) -1 ):3513(m),3390(m),3187(m),3090(w),3062(w),3029(w),2960(w),2928(w),2917(w),2851,(w),2745(w),1660(ν C＝N ,m),1628(ν C＝N ,m),1587(s),1515(w),1494(s),1437(s),1383(w),1350(w),1278(m),1227(m),1185(s),1153(w),1100(w),1079 (s),1055(w),1031(s),991(s),948(w),921(m),884(s),858(m),824(m),799(w),771(s),739(s),698(s).Elemental analysis: C 50 H 32 Theoretical values ​​for Br2Cl2F2N2Ni(988.22): C, 60.77; H, 3.26; N, 2.83. Experimental values: C, 60.96; H, 3.51; N, 3.01.

[0221] Example 14

[0222] The intermediate [1-(2,6-dimethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] acenaphthene chloride, as shown in formula (I), is denoted as complex Ni6.

[0223] At room temperature, NiCl₂·6H₂O (0.043 g, 0.18 mmol) and ligand L1 (0.11 g, 0.18 mmol) were mixed and dissolved in a mixed solution of ethanol (4 mL) and dichloromethane (5 mL). The mixture was stirred for 12 h under nitrogen protection. After removing the solvent under reduced pressure, anhydrous diethyl ether (7 mL) and n-hexane (15 mL) were added to induce precipitation, from which a red solid precipitated. The solid was filtered, washed with n-hexane, and dried to give 0.13 g of a light brown solid complex Ni₆. Yield: 85%.

[0224] The structural verification data is as follows:

[0225] FT-IR (cm) -1):3513(m),3390(m),3187(m),3066(w),3058(w),3026(w),2960(w),2851(w),2838(w),1661(ν C＝N ,m),1628(ν C＝N ,m),1587(s),1492(m),1440(s),1352(w),1329(w),1287(m),1262(w),12 50(m),1226(m),1186(m),1150(w),1122(m),1092(m),1050(m),1031(m),991( m),950(w),921(m),886(m),859(m),826(m),803(w),772(s),739(m),700(s).

[0226] Elemental analysis: C 39 H 28 Theoretical values ​​for Cl3FN2Ni(708.71): C, 66.10; H, 3.98; N, 3.95. Experimental values: C, 66.31; H, 3.85; N, 4.0.

[0227] Example 15

[0228] The intermediate [1-(2,6-diethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] acenaphthene chloride, as shown in formula (I), is denoted as complex Ni7.

[0229] Ni7 was prepared according to the method in Example 14, except that an equimolar amount of L2 was used to replace L1. Yield: 87%. Structural confirmation data are as follows:

[0230] FT-IR (cm) -1 ):3511(m),3421(m),3387(m),3183(m),3062(m),3026(m),2962(w),2932(w),2873(w),1656(ν C＝N ,m),1626(ν C＝N ,m),1587(s),1492(m),1439(s),1415(m),1383(m),1358(m),1327(m),1288(m),1186(s) ),1099(s),1032(w),991(w),950(w),921(w),810(w),774(s),741(s),700(s),676(w).

[0231] Elemental analysis: C41 H 32 Theoretical values ​​for Cl3FN2Ni (736.76): C, 66.84; H, 4.38; N, 3.80. Experimental values: C, 67.03; H, 4.43; N, 3.75.

[0232] Example 16

[0233] The intermediate [1-(2,6-diisopropylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] acenaphthene chloride shown in formula (I) is denoted as complex Ni8.

[0234] Ni8 was prepared according to the method in Example 14, except that an equimolar amount of L3 was used to replace L1. Yield: 84%. Structural confirmation data are as follows:

[0235] FT-IR (cm) -1 ):3511(s),3423(m),3387(w),2965(m),2951(w),2925(w),2873(w),2734(w),1655(ν C＝N ,m),1627(ν C＝N ,m),1588(s),1493(m),1474(w)1442(s),1377(w),1353(w),1324(w),1289(s),1256(w),1226(w),1186(s),1150(w) ),1150(w),1096(m),1121(w),1079(s),1031(s),994(m),947(m),923(w),830(m),807(w),774(s),742(s),701(s).

[0236] Anal.calcd for C 43 H 36 Cl3FN2Ni(764.82):C,67.53;H,4.74;N,3.66.Found C,67.37;H,4.49;N,3.60.

[0237] Elemental analysis: C 43 H 36 Theoretical values ​​for Cl3FN2Ni (764.82): C, 67.53; H, 4.74; N, 3.66. Experimental values: C, 67.37; H, 4.49; N, 3.60.

[0238] Example 17

[0239] The intermediate [1-(2,4,6-trimethylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] acenaphthene chloride shown in formula (I) is denoted as complex Ni9.

[0240] Ni9 was prepared according to the method in Example 14, except that an equimolar amount of L4 was used to replace L1. Yield: 86%. Structural confirmation data are as follows:

[0241] FT-IR (cm) -1 ):3497(m),3390(m),3058(w),3024(m),2962(w),2928(w),2870(m),2849(w),2730(w),1658(ν C＝N ,m),1626(ν C＝N ,m),1586(s),1494(s),1440(s),1379(m),1351(w),1337(m),1287(s),1237(m),1233(w),1227(w),1224(m),1188(w),1154 (w),1103(w),1054(m),1046(m),1031(s),990(m),954(w)921(m),885(s),853(s),830(s),809(w)774(s),738(s),700(s).

[0242] Elemental analysis: C 40 H 30 Theoretical values ​​for Cl3FN2Ni (722.74): C, 66.48; H, 4.18; N, 3.88. Experimental values: C, 66.50; H, 4.15; N, 3.80.

[0243] Example 18

[0244] The intermediate [1-(2,6-diethyl-4-methylphenylimine)-2-(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] acenaphthene chloride, as shown in formula (I), is denoted as complex Ni10.

[0245] Ni10 was prepared according to the method in Example 14, except that L1 was replaced with an equimolar amount of L5. Yield: 82%. Structural confirmation data are as follows:

[0246] FT-IR (cm) -1 ):3508(m),3391(m),3086(m),2962(w),3050(w),2952(w),2870(w),1657(ν C＝N,m),1625(ν C＝N ,m),1587(s),1494(s),1441(s),1383(w),1351(m),1331(m),1287(s),1228(s),1188(s),1154(m),1125(w),1103(s),1082(s) ,1046(m),1031(s),1016(w),990(s),954(m)922(m),885(s),874(m)858(s),830(s),814(w),800(w),775(s),740(s),701(s).

[0247] Elemental analysis: C 42 H 34 Theoretical values ​​for Cl3FN2Ni (750.79): C, 67.19; H, 4.56; N, 3.73. Experimental values: C, 67.36; H, 4.63; N, 3.80.

[0248] A mixed solution of diethyl ether and hexane (v:v = 2:1) was diffused into a saturated dichloromethane solution of the complex using a slow diffusion method at room temperature, resulting in the growth of Ni10(H2O) single crystals suitable for X-ray diffraction. For clarity, all hydrogen atoms in the complex molecular structure were omitted from the ORTEP diagram; the perspective view of the crystal molecular structure is shown below. Figure 2 As shown, it is a dimer with an asymmetric structure, and the coordinating atoms exhibit a distorted octahedral geometry around each nickel center.

[0249] Example 19

[0250] The intermediate [bis(2-diphenylmethyl-6-chloro-4-fluorophenylimine)acenaphthene] acenaphthene chloride shown in formula (II) is denoted as complex Ni12, wherein R 1 For chlorine, R 2 It is fluorine, R 3 It is hydrogen.

[0251] Ni12 was prepared according to the method in Example 14, except that an equimolar amount of L6 was used to replace L1. Yield: 82%. Structural confirmation data are as follows:

[0252] FT-IR (cm) -1 ):3510(m),3371(m),3181(w),3090(m),3062(m),3031(m),2955(w),2937(w),2866(w),1656(ν C＝N ,m),1629(ν C＝N,m),1584(s),1492(m),1455(m),1448(m),1434(s),1355(w),1327(w),1289(m),1223(m),1188(s),1156( w)1106(m),1082(s),1048(m)1030(m),987(s),947(w),920(s),861(s).824(s),771(s),739(s),698(s).

[0253] Elemental analysis: C 50 H 32 Theoretical values ​​for Cl4F2N2Ni (899.31): C, 66.78; H, 3.59; N, 3.12. Experimental values: C, 66.49; H, 3.48; N, 3.08.

[0254] Example 20:

[0255] The complex Ni1 (main catalyst) prepared in Example 9 and the co-catalyst MMAO were used to co-catalyze ethylene polymerization under high pressure (10 atm):

[0256] a) The ethylene polymerization process was carried out in a 250 mL stainless steel autoclave equipped with a pressure control system, temperature controller, and mechanical stirrer. The autoclave was evacuated and backfilled with nitrogen three times, followed by ethylene backfilling once. When the reactor reached 30 °C, toluene (25 mL) and a Ni1 solution (2 μmol) dissolved in toluene (25 mL) were added sequentially. Then, 2.44 mL of the co-catalyst MMAO (2.45 mol / L, n-heptane solution) and toluene (50 mL) were added, at which point the Al:Ni molar ratio was approximately 3000:1. Ethylene was then continuously introduced, and the mixture was stirred at a speed of 400 rpm while maintaining an ethylene pressure of P(C2H4) = 10 atm. The polymerization time was 30 min, and the polymerization temperature was 30 °C. After the reaction was completed, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The resulting mixture was quenched with a 15% (w / w) hydrochloric acid-ethanol solution, and the polymer was collected by filtration. After vacuum drying at 50 °C for 8 hours, the polymer was weighed.

[0257] The polymerization activity is 7.80 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =122.25℃, Mw=1.42×10 5 g·mol -1 PDI = 1.99. b) Basically the same as in Example 20a), except that 1.63 mL of co-catalyst MMAO is added, at which point the Al:Ni molar ratio is approximately 2000:1.

[0258] The polymerization activity is 4.63 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =115.64℃, Mw=0.72×10 5 g·mol -1 PDI = 2.62. c) Basically the same as in Example 20a), except that 2.04 mL of co-catalyst MMAO is added, at which point the Al:Ni molar ratio is approximately 2500:1.

[0259] The polymerization activity is 7.80 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =114.32℃, Mw=0.87×10 5 g·mol -1 PDI = 2.29. d) Basically the same as in Example 20a), except that 2.24 mL of co-catalyst MMAO is added, at which point the Al:Ni molar ratio is approximately 2750:1.

[0260] The polymerization activity is 8.05 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =112.84℃, Mw=1.04×10 5 g·mol -1 PDI = 2.34. e) Basically the same as in Example 20a), except that 2.85 mL of co-catalyst MMAO is added, at which point the Al:Ni molar ratio is approximately 3500:1.

[0261] The polymerization activity is 6.90 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =108.23℃, Mw=0.73×10 5 g·mol -1 PDI = 1.92. f) Basically the same as in Example 20a), except that the polymerization temperature is 40°C.

[0262] The polymerization activity is 8.06 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 Polymer T m =119.95℃, Mw=1.09×10 5 g·mol -1PDI = 1.82.

[0263] g) is basically the same as in Example 20a), except that the polymerization temperature is 50°C.

[0264] The polymerization activity is 8.18 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =114.93℃, Mw=0.93×10 5 g·mol -1 PDI = 1.87. h) is basically the same as in Example 20a), except that the polymerization temperature is 60°C.

[0265] The polymerization activity is 10.20 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =111.41℃, Mw=0.85×10 5 g·mol -1 PDI = 1.83. 50 mg of the polymer obtained in Example 20 (20 h) was dissolved in 0.5 mL of deuterated o-dichlorobenzene, and the polymer was tested at 100 °C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 31 / 1000 Cs (see NMR spectrum for details). Figure 3 ).

[0266] i) Basically the same as in Example 20a), except that the polymerization temperature is 70°C.

[0267] The polymerization activity is 8.68 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =114.07℃, Mw=0.70×10 5 g·mol -1 PDI = 2.33. j) Basically the same as in Example 20a), except that the polymerization temperature is 80°C.

[0268] The polymerization activity is 3.30 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =115.02℃, Mw=0.65×10 5 g·mol -1PDI = 2.09. k) is basically the same as in Example 20h, except that the polymerization pressure is 5 atm.

[0269] The polymerization activity is 5.20 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =99.37℃, Mw=0.64×10 5 g·mol -1 PDI = 1.76. l) is basically the same as in Example 20h, except that the polymerization pressure is 1 atm.

[0270] The polymerization activity is 0.32 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 Mw = 0.35 × 10 5 g·mol -1 PDI = 1.83.

[0271] m) is basically the same as 20h in this embodiment, except that the reaction time is 5min.

[0272] The polymerization activity is 72.40 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =109.34℃, Mw=0.77×10 5 g·mol -1 PDI = 1.76. n) is basically the same as in this example 20h), the only difference being that the reaction time is 15min.

[0273] The polymerization activity is 25.90 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =110.12℃, Mw=0.74×10 5 g·mol -1 PDI = 1.91. (o) Basically the same as in this example 20h), the only difference is that the reaction time is 45min.

[0274] The polymerization activity is 7.00 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =111.87℃, Mw=0.64×10 5 g·mol -1 PDI = 1.79. Example 21:

[0275] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni2 and co-catalyst MMAO:

[0276] The process is basically the same as in Example 20h, except that Ni2 is used as the main catalyst. The polymerization activity is 8.43 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =97.44℃, Mw=0.94×10 5 g·mol -1 PDI = 1.81.

[0277] Example 22:

[0278] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni3 and co-catalyst MMAO:

[0279] The process is basically the same as in Example 20h, except that Ni3 is used as the main catalyst. The polymerization activity is 7.71 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 Polymer T m =96.50℃, Mw=1.80×10 5 g·mol -1 PDI = 2.50.

[0280] 50 mg of the polymer obtained in Example 22 was dissolved in 0.5 mL of 1,1,2,2-tetrachloroethane. The polymer was tested at 100 °C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 50 / 1000 Cs (see NMR spectrum for details). Figure 4 ).

[0281] The polyethylene obtained in Example 22 was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 17.3 MPa, and the elongation at break was 1373%. The obtained polymer was subjected to stress-strain recovery testing, and the elastic recovery rate was 57% (see mechanical property test spectrum for details). Figure 10 ,as well as Figure 11 The corresponding curve (b) in the graph.

[0282] Example 23:

[0283] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni4 and co-catalyst MMAO:

[0284] The process is basically the same as in Example 20h, except that Ni4 is used as the main catalyst. The polymerization activity is 11.20 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =98.00℃, Mw=0.55×10 5 g·mol -1 PDI = 1.67.

[0285] Example 24:

[0286] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni5 and co-catalyst MMAO:

[0287] The process is basically the same as in Example 20h, except that Ni5 is used as the main catalyst. Polymerization activity: 6.02 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =95.84℃, Mw=1.08×10 5 g·mol -1 PDI = 1.83.

[0288] Example 25:

[0289] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni11 and co-catalyst MMAO:

[0290] The process is basically the same as in Example 20h, except that Ni11 is used as the main catalyst. The polymerization activity is 10.20 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =102.60℃, Mw=2.52×10 5 g·mol -1 PDI = 1.87.

[0291] Take 50 mg of the polymer obtained in Example 25, dissolve it in 0.5 mL of 1,1,2,2-tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 44 / 1000 Cs (see NMR spectrum for details). Figure 5 ).

[0292] The polyethylene obtained in Example 25 was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 25.3 MPa, and the elongation at break was 1255%. The obtained polymer was subjected to stress-strain recovery testing, and the elastic recovery rate was 55% (see the mechanical property test spectrum for details). Figure 10 ,as well as Figure 11 The corresponding curve in (c).

[0293] Example 26:

[0294] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni6 and co-catalyst MMAO:

[0295] The process is basically the same as in Example 20h, except that Ni6 is used as the main catalyst. The polymerization activity is 6.97 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =104.60℃, Mw=0.69×10 5 g·mol -1 PDI = 2.45.

[0296] Example 27:

[0297] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni7 and co-catalyst MMAO:

[0298] The process is basically the same as in Example 20h, except that Ni7 is used as the main catalyst. The polymerization activity is 7.48 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 Polymer T m =97.72℃, Mw=1.22×10 5 g·mol -1 PDI = 1.89.

[0299] Example 28:

[0300] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni8 and co-catalyst MMAO:

[0301] The process is basically the same as in Example 20h, except that Ni8 is used as the main catalyst. The polymerization activity is 14.60 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =102.51℃, Mw=1.63×10 5 g·mol -1 PDI = 1.65.

[0302] Example 29:

[0303] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni9 and co-catalyst MMAO:

[0304] The process is basically the same as in Example 20h, except that Ni9 is used as the main catalyst. Polymerization activity: 9.43 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =101.10℃, Mw=0.66×10 5 g·mol -1 PDI = 2.17.

[0305] Example 30:

[0306] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni10 and co-catalyst MMAO:

[0307] The process is basically the same as in Example 20h, except that Ni10 is used as the main catalyst. The polymerization activity is 7.63 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =90.56℃, Mw=1.14×10 5 g·mol -1 PDI = 1.71.

[0308] Example 31:

[0309] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni12 and co-catalyst MMAO:

[0310] The process is basically the same as in Example 20h, except that Ni12 is used as the main catalyst. Polymerization activity: 5.46 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =119.50℃, Mw=2.25×10 5 g·mol -1 PDI = 2.29.

[0311] Example 32:

[0312] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni1 and co-catalyst MMAO:

[0313] The process is basically the same as in Example 20h, except that hexane is used as the polymerization solvent. The polymerization activity is 10.30 × 10⁻⁶.6 g·mol -1 (Ni)·h -1 T m =114.30℃, Mw=1.19×10 5 g·mol -1 PDI = 2.04.

[0314] Example 33:

[0315] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni2 and co-catalyst MMAO:

[0316] The process is basically the same as in Example 21), except that hexane is used as the polymerization solvent. The polymerization activity is 9.80 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =96.80℃, Mw=0.96×10 5 g·mol -1 PDI = 1.62.

[0317] Example 34:

[0318] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni3 and co-catalyst MMAO:

[0319] The process is basically the same as in Example 22), except that hexane is used as the polymerization solvent. The polymerization activity is 7.92 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =103.20℃, Mw=2.36×10 5 g·mol -1 PDI = 2.29.

[0320] Example 35:

[0321] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni4 and co-catalyst MMAO:

[0322] The process is basically the same as in Example 23), except that hexane is used as the polymerization solvent. The polymerization activity is 12.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =101.90℃, Mw=0.76×10 5 g·mol -1 PDI = 1.77.

[0323] Example 36:

[0324] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni5 and co-catalyst MMAO:

[0325] The process is basically the same as in Example 24, except that hexane is used as the polymerization solvent. The polymerization activity is 11.80 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =90.44℃, Mw=1.13×10 5 g·mol -1 PDI = 1.71.

[0326] Example 37:

[0327] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni11 and co-catalyst MMAO:

[0328] The process is basically the same as in Example 25, except that hexane is used as the polymerization solvent. The polymerization activity is 7.52 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =111.70℃, Mw=2.80×10 5 g·mol -1 PDI = 2.16.

[0329] Example 38:

[0330] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni6 and co-catalyst MMAO:

[0331] The process is basically the same as in Example 26, except that hexane is used as the polymerization solvent. The polymerization activity is 12.70 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =107.10℃, Mw=0.79×10 5 g·mol -1 PDI = 1.97.

[0332] Example 39:

[0333] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni7 and co-catalyst MMAO:

[0334] The process is basically the same as in Example 27, except that hexane is used as the polymerization solvent. The polymerization activity is 10.10 × 10⁻⁶. 6 g·mol -1 (Ni)·h-1 T m =88.77℃, Mw=0.96×10 5 g·mol -1 PDI = 1.71.

[0335] Example 40:

[0336] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni8 and co-catalyst MMAO:

[0337] The process is basically the same as in Example 28, except that hexane is used as the polymerization solvent. The polymerization activity is 8.25 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =106.50℃, Mw=1.90×10 5 g·mol -1 PDI = 2.05.

[0338] Example 41:

[0339] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni9 and co-catalyst MMAO:

[0340] The process is basically the same as in Example 29, except that hexane is used as the polymerization solvent. The polymerization activity is 17.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =102.60℃, Mw=0.91×10 5 g·mol -1 PDI = 1.37.

[0341] Example 42:

[0342] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni10 and co-catalyst MMAO:

[0343] The process is basically the same as in Example 30, except that hexane is used as the polymerization solvent. The polymerization activity is 10.60 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =113.00℃, Mw=1.33×10 5 g·mol -1 PDI = 1.98.

[0344] Example 43:

[0345] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni12 and co-catalyst MMAO:

[0346] The process is basically the same as in Example 31), except that hexane is used as the polymerization solvent. The polymerization activity is 10.20 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =112.20℃, Mw=3.06×10 5 g·mol -1 PDI = 2.22.

[0347] Example 44:

[0348] Ethylene polymerization was co-catalyzed under high pressure (10 atm) using 2 μmol of complex Ni1 and co-catalyst Et2AlCl (DEAC). The polymerization process was carried out in a 250 mL stainless steel autoclave equipped with a pressure control system, temperature controller, and mechanical stirrer. The autoclave was evacuated and backfilled with nitrogen three times, followed by ethylene backfilling once. When the reactor reached 55 °C, toluene (25 mL) and a 2 μmol Ni1 solution dissolved in toluene (25 mL) were added sequentially. Then, 2.4 mL of co-catalyst Et2AlCl (0.5 mol / L, toluene solution) and 50 mL of toluene were added, resulting in an Al:Ni molar ratio of approximately 600:1. Ethylene was continuously introduced, and the mixture was stirred at 400 rpm while maintaining an ethylene pressure of P(C2H4) = 10 atm for 30 min at a polymerization time of 55 °C. After the reaction was complete, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The resulting mixture was quenched with a 15% hydrochloric acid-ethanol solution, filtered, and the polymer was collected. After vacuum drying at 50°C for 8 hours, the polymer was weighed.

[0349] The polymerization activity is 13.80 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =97.04℃, Mw=0.71×10 5 g·mol -1 PDI = 1.69. 50 mg of the polymer obtained in Example 44) was dissolved in 0.5 mL of 1,1,2,2-tetrachloroethane, and the polymer was tested at 100°C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 54 / 1000 Cs (see NMR spectrum for details). Figure 6 ).

[0350] Example 45:

[0351] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni2 and co-catalyst DEAC:

[0352] The process is basically the same as in Example 44, except that Ni2 is used as the main catalyst. The polymerization activity is 9.92 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =84.58℃, Mw=0.89×10 5 g·mol -1 PDI = 1.68.

[0353] Example 46:

[0354] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni3 and co-catalyst DEAC:

[0355] The process is basically the same as in Example 44, except that Ni3 is used as the main catalyst. The polymerization activity is 9.39 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 Polymer T m =91.79℃, Mw=1.26×10 5 g·mol -1 PDI = 1.91.

[0356] Take 50 mg of the polymer obtained in Example 46, dissolve it in 0.5 mL of 1,1,2,2-tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 96 / 1000 Cs (see NMR spectrum for details). Figure 7 ).

[0357] Example 47:

[0358] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni4 and co-catalyst DEAC:

[0359] The process is basically the same as in Example 44, except that Ni4 is used as the main catalyst. The polymerization activity is 12.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =58.98℃, Mw=0.56×105 g·mol -1 PDI = 1.77.

[0360] Example 48:

[0361] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni5 and co-catalyst DEAC:

[0362] Basically the same as Example 44), except that Ni5 is used as the main catalyst. Polymerization activity: 8.90 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =79.24℃, Mw=1.01×10 5 g·mol -1 PDI = 1.82.

[0363] Example 49:

[0364] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni11 and co-catalyst DEAC:

[0365] The process is basically the same as in Example 44, except that Ni11 is used as the main catalyst. The polymerization activity is 8.80 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =114.67℃, Mw=1.52×10 5 g·mol -1 PDI = 2.12.

[0366] Take 50 mg of the polymer obtained in Example 49), dissolve it in 0.5 mL of 1,1,2,2-tetrachloroethane, and test the polymer at 100°C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 70 / 1000 Cs (see NMR spectrum for details). Figure 8 ).

[0367] The polyethylene obtained in Example 49) was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 14.1 MPa, and the elongation at break was 1635%. The obtained polymer was subjected to stress-strain recovery testing, and the elastic recovery rate was 62% (see the mechanical property test spectrum for details). Figure 10 ,as well as Figure 11 The corresponding curve in the graph is (a).

[0368] Example 50:

[0369] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni6 and co-catalyst DEAC:

[0370] The process is basically the same as in Example 44), except that Ni6 is used as the main catalyst. The polymerization activity is 11.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =99.14℃, Mw=0.70×10 5 g·mol -1 PDI = 1.88.

[0371] Example 51:

[0372] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni7 and co-catalyst DEAC:

[0373] The process is basically the same as in Example 44, except that Ni7 is used as the main catalyst. The polymerization activity is 10.00 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 Polymer T m =94.86℃, Mw=1.22×10 5 g·mol -1 PDI = 1.89.

[0374] Example 52:

[0375] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni8 and co-catalyst DEAC:

[0376] The process is basically the same as in Example 44, except that Ni8 is used as the main catalyst. The polymerization activity is 8.93 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =94.12℃, Mw=0.84×10 5 g·mol -1 PDI = 1.86.

[0377] Example 53:

[0378] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni9 and co-catalyst DEAC:

[0379] Basically the same as Example 44), except that Ni9 is used as the main catalyst. Polymerization activity: 9.43 × 10⁻⁶ 6 g·mol -1 (Ni)·h-1 Polymer T m =95.40℃, Mw=0.91×10 5 g·mol -1 PDI = 1.47.

[0380] Example 54:

[0381] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni10 and co-catalyst DEAC:

[0382] The process is basically the same as in Example 44), except that Ni10 is used as the main catalyst. The polymerization activity is 10.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =97.27℃, Mw=1.11×10 5 g·mol -1 PDI = 1.91.

[0383] Example 55:

[0384] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni12 and co-catalyst DEAC:

[0385] Basically the same as Example 44), except that Ni12 is used as the main catalyst. Polymerization activity: 6.43 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =108.49℃, Mw=1.53×10 5 g·mol -1 PDI = 2.06.

[0386] Example 56:

[0387] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni1 and co-catalyst DEAC:

[0388] The process is basically the same as in Example 44), except that hexane is used as the polymerization solvent. The polymerization activity is 13.90 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =111.60℃, Mw=0.99×10 5 g·mol -1 PDI = 1.88.

[0389] Example 57:

[0390] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni2 and co-catalyst DEAC:

[0391] The process is basically the same as in Example 45, except that hexane is used as the polymerization solvent. The polymerization activity is 11.10 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =92.59℃, Mw=1.15×10 5 g·mol -1 PDI = 1.64.

[0392] Example 58:

[0393] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni3 and co-catalyst DEAC:

[0394] The process is basically the same as in Example 46), except that hexane is used as the polymerization solvent. The polymerization activity is 9.38 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =104.90℃, Mw=1.68×10 5 g·mol -1 PDI = 1.62.

[0395] Example 59:

[0396] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni4 and co-catalyst DEAC:

[0397] The process is basically the same as in Example 47), except that hexane is used as the polymerization solvent. The polymerization activity is 12.60 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =87.10℃, Mw=0.58×10 5 g·mol -1 PDI = 1.85.

[0398] Example 60:

[0399] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni5 and co-catalyst DEAC:

[0400] The process is basically the same as in Example 48, except that hexane is used as the polymerization solvent. The polymerization activity is 12.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m=99.41℃, Mw=1.58×10 5 g·mol -1 PDI = 1.74.

[0401] Example 61:

[0402] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni11 and co-catalyst DEAC:

[0403] The process is basically the same as in Example 49), except that hexane is used as the polymerization solvent. The polymerization activity is 9.77 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =115.10℃, Mw=2.10×10 5 g·mol -1 PDI = 2.03.

[0404] Take 50 mg of the polymer obtained in Example 61), dissolve it in 0.5 mL of 1,1,2,2-tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2048 times yielded peak shifts between 20-40 ppm, indicating shifts in methyl, methylene, and methine groups, confirming the obtained polymer is branched polyethylene with a branching degree of 50 / 1000 Cs (see NMR spectrum for details). Figure 9 ).

[0405] Example 62:

[0406] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni6 and co-catalyst DEAC:

[0407] The process is basically the same as in Example 50, except that hexane is used as the polymerization solvent. The polymerization activity is 12.70 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =95.48℃, Mw=1.01×10 5 g·mol -1 PDI = 2.03.

[0408] Example 63:

[0409] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni7 and co-catalyst DEAC:

[0410] The process is basically the same as in Example 51), except that hexane is used as the polymerization solvent. The polymerization activity is 10.80 × 10⁻⁶. 6 g·mol-1 (Ni)·h -1 T m =81.35℃, Mw=1.47×10 5 g·mol -1 PDI = 2.12.

[0411] Example 64:

[0412] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni8 and co-catalyst DEAC:

[0413] The process is basically the same as in Example 52), except that hexane is used as the polymerization solvent. The polymerization activity is 12.40 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =114.90℃, Mw=1.93×10 5 g·mol -1 PDI = 2.02.

[0414] Example 65:

[0415] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni9 and co-catalyst DEAC:

[0416] The process is basically the same as in Example 53, except that hexane is used as the polymerization solvent. The polymerization activity is 14.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =88.02℃, Mw=0.91×10 5 g·mol -1 PDI = 1.92.

[0417] Example 66:

[0418] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni10 and co-catalyst DEAC:

[0419] The process is basically the same as in Example 54, except that hexane is used as the polymerization solvent. The polymerization activity is 11.20 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =109.00℃, Mw=1.65×10 5 g·mol -1 PDI = 2.03.

[0420] Example 67:

[0421] Co-catalytic polymerization of ethylene under high pressure (10 atm) using Ni12 and co-catalyst DEAC:

[0422] The process is basically the same as in Example 55, except that hexane is used as the polymerization solvent. The polymerization activity is 6.50 × 10⁻⁶. 6 g·mol -1 (Ni)·h -1 T m =119.20℃, Mw=2.72×10 5 g·mol -1 PDI = 2.22.

[0423] Comparative Example 1

[0424] Under the same test conditions as Example 20h of this application (other reaction conditions remain unchanged, only Ni1 in 20h is replaced with Formulas 2-1 and 3-1 respectively), the catalytic activity of Equations 2-1 and 3-1 is tested, and the catalytic results are as follows:

[0425] Formula 2-1: Polymerization activity is 2.71 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 T m =44.11℃, Mw=2.54×10 5 g·mol -1 PDI = 2.31.

[0426] Formula 3-1: Polymerization activity is 4.59 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 T m =38.93℃, Mw=3.72×10 5 g·mol -1 PDI = 2.28.

[0427]

[0428] Comparative Example 2

[0429] The catalytic activity of Ni1 in this application with the complexes of formulas 2-1 and 3-1 above was tested under the same conditions at 20°C. Other reaction conditions remained unchanged, except that Ni1 in 20°C was replaced with formulas 2-1 and 3-1 as follows. The catalytic results are as follows:

[0430] Formula 2-1: Polymerization activity is 1.86 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 T m=45.19℃, Mw=2.61×10 5 g·mol -1 PDI = 2.22.

[0431] Formula 3-1: Polymerization activity is 2.71 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 T m =40.20℃, Mw =3.76×10 5 g·mol -1 PDI = 2.36.

[0432] The catalytic lifetimes of the Ni1 complex of this application are compared with those of the comparative formulas 2-1 and 3-1, as shown in Table 1.

[0433] Table 1

[0434]

[0435] The test data above show that modifying the catalyst of this application at different substitution sites of the N-aryl group, especially introducing halogen atoms at the para or ortho position, can yield a highly active nickel catalyst with better stability in olefin polymerization. Compared with the catalysts prepared by Formulas 2 and 3, the polymer catalyzed by the catalyst of this application exhibits higher TT. m Higher strength means higher polymer strength. Lower molecular weight and narrower molecular weight distribution make it more advantageous for subsequent processing.

[0436] It is readily understood that the above embodiments are merely illustrative examples for clear explanation and do not imply that the invention is limited thereto. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. Nickel complexes containing polyhalogen-substituted acenaphthene groups as shown in formula (I) or formula (II): in, R 1 R 2 They may be the same or different, each independently selected from fluorine, chlorine, or bromine; R 3 R 4 R 5 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 alkyl; R 6 R 7 R 8 R 9 R 10 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 alkyl; X may be the same or different, and each is independently selected from Cl, Br or I.

2. The nickel complex containing polyhalogen-substituted acenaphthene α-diimine according to claim 1, wherein, R 1 R 2 Whether they are the same or different, they are each independently selected from fluorine or chlorine; R 3 R 4 R 5 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 alkyl; R 6 R 7 R 8 R 9 R 10 Whether the groups are the same or different, they are each independently selected from H, nitro, fluorine, chlorine, bromine, and C. 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 alkyl; X may be the same or different, and each is independently selected from Cl, Br or I.

3. The nickel complex containing polyhalogen-substituted acenaphthene α-diimine according to claim 1 or 2, wherein, R 1 Selected from Cl; R 2 Selected from F;R 3 R 4 R 5 R 9 R 10 Selected from H; R 6 R 7 R 8 Whether the two are the same or different, they are selected independently from H and C. 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 alkyl; X is the same, and is selected from Cl, Br, or I.

4. The nickel complex containing polyhalogen-substituted acenaphthene α-diimine according to any one of claims 1-3, wherein, The polyhalogen-substituted acenaphthene α-diimine nickel complex shown in formula (I) has the structures shown in formulas (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), (I-9), or (I-10): All other substituents are H; The nickel complex containing polyhalogen-substituted acenaphthene α-diimine shown in formula (II) has the structure shown in formula (II-1) or formula (II-2):

5. The intermediate compound represented by formula (III) or formula (IV): in, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 It has the definition as described in any one of claims 1-3; Preferably, the intermediate compound has the structure shown in formula (III-1), (III-2), (III-3), (III-4), (III-5), or (IV-1):

6. The method for preparing the nickel complex containing polyhalogen-substituted acenaphthene α-diimine according to any one of claims 1-4, wherein, The steps include the following: The intermediate compound of formula (III) or (IV) according to claim 5 is reacted with a nickel-containing compound to obtain the nickel complex of formula (I) or (II) containing a polyhalogen-substituted acenaphthene α-diimide.

7. A catalyst composition comprising a main catalyst and an optional co-catalyst; said main catalyst comprising one or more of the polyhalogen-substituted acenaphthene α-diimine nickel complexes according to any one of claims 1-4.

8. The catalyst composition according to claim 7, wherein, The cocatalyst is selected from one or more of aluminoxane, alkylaluminum, and alkylaluminum chloride.

9. The use of the catalyst composition of claim 7 or 8 in the catalytic polymerization of olefins.

10. A method for preparing polyethylene, wherein, The catalyst composition of claim 7 or 8 is used to catalyze the polymerization of ethylene to prepare polyethylene.

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