An unsymmetrical dinuclear nickel complex containing heteroligand and its preparation method and use

Abstract

This invention provides an asymmetric binuclear nickel complex containing heteroligands, having the structure shown in formula (I). This invention also provides a method for preparing the binuclear nickel complex and its uses. Furthermore, this invention provides a catalyst composition and a method for olefin polymerization, particularly for preparing polyethylene. The binuclear nickel complex provided by this invention has a novel structure and exhibits advantages such as high catalytic activity and good thermal stability when used to catalyze olefin polymerization (especially ethylene polymerization). Moreover, the two active centers have different catalytic behaviors and can work synergistically, thus enabling the preparation of bimodal branched polyethylene materials with excellent performance. In addition, the method for preparing the binuclear nickel complex provided by this invention is simple, the reaction conditions are mild, the operation is simple and easy to control, and it has strong industrial applicability.

Description

Technical Field

[0001] This invention relates to the field of olefin catalytic polymerization technology, specifically to an asymmetric binuclear nickel complex containing heteroligands, its preparation method and uses, and also to a catalyst composition comprising the binuclear nickel complex and an olefin polymerization method, particularly a method for preparing polyethylene. Background Technology

[0002] Brookhart-type α-diimine nickel complexes (A, Formula 1), as typical post-transition metal complexes capable of catalyzing the preparation of branched polyethylene from pure ethylene (J. Am. Chem. Soc., 1995, 117, 6414), have received widespread attention and in-depth research from scholars over the past two decades. The structure and type of ligands often directly determine the catalytic performance of the complex, and a large part of ligand structural modification focuses on the systematic modification of the ligand skeleton and N-aryl substituents. In terms of steric and electronic effects, changes in the type of N-aryl substituents directly affect the coordination state and properties of the metal center, thereby regulating the catalytic activity, thermal stability, and molecular weight and microstructure of the resulting polyethylene. Furthermore, changes in the ligand skeleton, such as changes in the substituents on the pyridine ring, improvements in the cycloalkylpyridine imine structure, and changes in the N-aryl structure (C and D, Formula 1) for the pyridine imine nickel complex (B, Formula 1), can all promote the realization of the multifunctional catalytic properties of the ligand skeleton, ultimately achieving the efficient preparation of highly selective LAO and branched polyethylene wax (Dalton Trans., 2022, 51, 14375).

[0003]

[0004] Inspired by the concept of synergistic effects of multi-metal centers, researchers have integrated N^N-type bidentate ligands into binuclear and even multi-nuclear nickel complex frameworks based on the structural design rules of mononuclear catalysts. This aims to study the relationship between the structure of multi-nuclear nickel complex catalysts and their catalytic performance. This multi-nuclear structural design further promotes the structural development and technological innovation of post-transition metal complex catalysts. The synergistic interactions of multi-nuclear nickel complexes are mainly manifested by increasing the local monomer concentration around the active center, thereby improving the catalytic activity and polymer molecular weight of the multi-nuclear catalyst. The interaction between polymer chains and adjacent metal centers may also contribute to this synergistic effect. The structure of multi-nuclear catalysts, such as the type and number of metal centers, the type and nature of bridging groups, and the type of ligand framework, collectively influence the catalytic behavior of multi-nuclear catalysts. Notably, structurally symmetrical multi-nuclear catalysts, such as the series of binuclear nickel complexes E (Equation 2) with symmetrical bridging groups (Coord. Chem. Rev., 2021, 434, 213788), tend to produce polyethylene products with narrow molecular weight distributions due to their uniform active center types.

[0005]

[0006] However, the high-molecular-weight and even ultra-high-molecular-weight polymers obtained from the above catalytic systems exhibit monodisperse properties and inert saturated CH bonds, thus facing various problems and difficulties in industrial-scale processing and polymer functionalization. For example, in the physical blending modification of traditional modified ultra-high-molecular-weight polyethylene, the large molecular weight difference between low-molecular-weight polyethylene and ultra-high-molecular-weight polyethylene easily leads to phase separation during physical blending modification, resulting in extremely low ultra-high-molecular-weight polyethylene blending amounts, which severely limits the mechanical properties of the product. To enhance the mixing of low-molecular-weight polyethylene and ultra-high-molecular-weight polyethylene and improve the mechanical properties of the product, in-situ polymerization modification based on multi-active-site catalyst design helps to promote uniform mixing between polymers at the nanoscale, thereby achieving the homogeneity of the final product. In addition, the structural symmetry of polynuclear nickel complexes also limits further understanding of the multi-active-site cooperation mode and further research on the catalytic mechanism of polynuclear nickel complexes. Summary of the Invention

[0007] Considering the advantages of bimodal polyethylene in polymer processing and in order to explore post-functionalization methods for saturated polyethylene, and further investigate how the synergistic effect of metal centers influences the catalytic behavior of heteroligand binuclear catalysts, the inventors proposed and synthesized a series of asymmetric binuclear nickel complexes based on pyridinium imine and acenaphthene α-diimine ligand frameworks. In the structure of these binuclear nickel complexes, the inventors selected substituted biphenyl groups as bridging groups and simultaneously modified the electronic properties of the N-aryl para-substituent groups on the other side to optimize the structure of the binuclear nickel complexes from both electronic and steric hindrance perspectives, thus leading to this invention. Furthermore, the inventors conducted detailed catalytic evaluations of the prepared series of binuclear nickel catalysts to determine the structural characteristics of the catalysts, the type of co-catalyst, and the effects of polymerization conditions on catalytic activity and polymer performance.

[0008] Therefore, one object of the present invention is to provide an asymmetric binuclear nickel complex containing heteroligands, which, when used as an olefin polymerization catalyst (especially an ethylene polymerization catalyst), exhibits high activity and high thermal stability. Moreover, the two active centers have different catalytic behaviors and can work synergistically, thus enabling the preparation of bimodal branched polyethylene materials with excellent performance.

[0009] Another object of the present invention is to provide a method for preparing the binuclear nickel complex and its uses.

[0010] The first aspect of the present invention provides an asymmetric binuclear nickel complex containing anisoligands, having the structure shown in formula (I):

[0011]

[0012] Among them, R 1 Same or different, R 3 Same or different, R 1 R 2 R 3 and R 4 Each of the following groups is independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxyl, mercapto, nitro, C3-C10 cycloalkyl or C6-C14 aryl, wherein the alkyl, alkoxy, hydroxyl or mercapto group is optionally substituted by one or more substituents selected from C1-C6 alkyl, C3-C10 cycloalkyl, C6-C14 aryl or R', wherein R' is selected from C3-C10 halocycloalkyl or C6-C14 haloaryl;

[0013] X is the same or different, and is selected from halogens.

[0014] In some preferred embodiments, the R 1 Same or different, selected from hydrogen or C1-C6 alkyl;

[0015] The R 2 Selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxyl, mercapto, nitro, C3-C10 cycloalkyl, C6-C14 aryl, -O-C3-C10 cycloalkyl, or -O-C6-C14 aryl, wherein the alkyl group is optionally substituted with 1 to 3 phenyl or halophenyl groups; for example, the R 2 Selected from hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, hydroxy, mercapto, nitro, trifluoromethoxy, fluorine, chlorine, bromine, iodine, cyclopropyl, cyclohexyl, phenyl, benzyl, diphenylmethyl or di(4-fluorophenyl)methyl;

[0016] The R 3 Same or different, selected from hydrogen or C1-C6 alkyl;

[0017] The R 4 Selected from hydrogen or C1-C6 alkyl groups;

[0018] The X may be the same or different, and is selected from fluorine, chlorine or bromine.

[0019] In some preferred embodiments, the R 1 Same or different, selected from hydrogen or C1-C6 alkyl, for example selected from hydrogen or C1-C4 alkyl;

[0020] The R 2 It is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy (preferably C1-C6 fluoroalkoxy), halogen, hydroxyl, mercapto or nitro, for example selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, fluorine, chlorine, bromine or nitro;

[0021] The R 3 Same or different, selected from C1 to C6 alkyl groups, for example, selected from C2 to C4 alkyl groups;

[0022] The R 4 Selected from C1 to C6 alkyl groups, for example, selected from C1 to C4 alkyl groups;

[0023] X is selected from chlorine or bromine, for example, from bromine;

[0024] In some preferred embodiments, the complex is selected from:

[0025]

[0026]

[0027]

[0028] Specifically, the complexes shown in the table above have the following group definitions:

[0029] C1:R 1 =H;R 2 =Me;R 3 = i Pr;R 4 =Me; X is Br;

[0030] C2:R 1 =H;R 2 = i Pr;R 3 = i Pr;R 4 =Me; X is Br;

[0031] C3:R 1 =H;R 2 = t Bu;R 3 = i Pr;R 4 =Me; X is Br;

[0032] C4:R 1 =H;R 2 =OMe;R 3 = i Pr;R 4 =Me; X is Br;

[0033] C5:R 1 =H;R 2 =OCF3;R 3 = i Pr;R 4 =Me; X is Br;

[0034] C6:R 1 =H;R 2 =Cl;R 3 = i Pr;R 4 =Me; X is Br;

[0035] C7:R 1 =H;R 2 =F;R 3 = i Pr;R 4 =Me; X is Br;

[0036] C8:R 1 =H;R 2 =NO2; R 3 = i Pr;R4 =Me; X is Br.

[0037] A second aspect of the present invention provides a method for preparing the asymmetric binuclear nickel complex containing heteroligands as described in any of the above-mentioned technical solutions, wherein the preparation method includes the following steps:

[0038] S1: The acenaphthene monoketone of the structure shown in formula (III) undergoes a ketamine condensation reaction with the benzidine of the structure shown in formula (IV) to obtain the acenaphthene diimine of the structure shown in formula (V);

[0039] S2: The acenaphthene diimide undergoes a ketamine condensation reaction with an acylpyridine of formula (VI) to obtain a ligand compound of formula (II); and

[0040] S3: The ligand compound undergoes a complexation reaction with a nickel-containing reagent to obtain the binuclear nickel complex;

[0041]

[0042]

[0043] Among them, R 1 R 2 R 3 and R 4 Each is independently defined as described in any of the above technical solutions.

[0044] In some preferred embodiments, the nickel-containing reagent is selected from nickel halides commonly found in the art, including but not limited to (DME)NiBr2, NiCl2·6H2O, NiBr2, etc.

[0045] In some preferred embodiments, in step S1, the acenaphthene monoketone and benzidine undergo a ketamine condensation reaction in a first organic solvent in the presence of a first catalyst;

[0046] In step S2, the acenaphthene diimide and acylpyridine undergo a ketamine condensation reaction in a second organic solvent in the presence of a second catalyst; and

[0047] In step S3, the ligand compound and the nickel-containing reagent undergo a complexation reaction in a third organic solvent.

[0048] In some preferred embodiments, the first organic solvent and the second organic solvent are each independently selected from aromatic organic solvents commonly used in the art, such as toluene.

[0049] In some preferred embodiments, the first catalyst and the second catalyst are each independently selected from ketamine condensation catalysts commonly used in the art, such as p-toluenesulfonic acid.

[0050] In some preferred embodiments, the molar ratio of acenaphthene monoketone to benzidine is 1:1 to 2, for example, 1:1.2 to 1.5.

[0051] In some preferred embodiments, the ketamine condensation reaction in step S1 is carried out under reflux for 6 to 24 hours, for example, under reflux for 6 to 12 hours.

[0052] In some preferred embodiments, the molar ratio of acenaphthene to acylpyridine is 1:1 to 10, for example, 1:1 to 5.

[0053] In some preferred embodiments, the ketamine condensation reaction in step S2 is carried out under reflux for 6 to 24 hours, for example, under reflux for 6 to 12 hours.

[0054] In some preferred embodiments, the third organic solvent is selected from one or more of the common halogenated alkanes and alcohols in the art, such as one or more of dichloromethane and ethanol.

[0055] In some more preferred embodiments, the molar ratio of the ligand compound to the nickel-containing reagent is 1:2 to 3, for example, 1:2 to 2.5.

[0056] In some preferred embodiments, the complexation reaction is carried out at a temperature of 0–35°C (e.g., 10–30°C, or even 20–25°C) and for a time of 8–16 h (e.g., 10–15 h).

[0057] In some preferred embodiments, the complexation reaction is carried out under anaerobic conditions, for example, under the protection of an inert gas such as nitrogen.

[0058] In some preferred embodiments, the ketamine condensation reaction is completed by the following purification process: the reaction system is decomposed to remove the organic solvent (e.g., the first organic solvent or the second organic solvent) to obtain the crude product, and then column chromatography (e.g., basic alumina column) is performed using a mixed solvent of petroleum ether and ethyl acetate (e.g., a volume ratio of 25:1 for step S1 and 50:1 for step S2) as the eluent. The desired fraction is collected, and the eluent is removed to obtain the purified target product.

[0059] In some preferred embodiments, the complexation reaction is completed by the following purification process: the reaction system is concentrated under reduced pressure (e.g., concentrated to dryness or to a small volume), then dissolved in an organic solvent (e.g., anhydrous diethyl ether), the resulting precipitate is separated, washed (e.g., washed 2 to 5 times with anhydrous diethyl ether) and dried (e.g., vacuum dried) to obtain the purified binuclear nickel complex.

[0060] In the preparation method provided by the present invention, the acenaphthenic monoketone with the structure shown in formula (III), the benzidine with the structure shown in formula (IV), and the acylpyridine with the structure shown in formula (VI) can all be obtained commercially or can be prepared by referring to the literature, such as the preparation process of acenaphthenic monoketone disclosed in Chinese Patent CN 108794545B.

[0061] For example, the acenaphthene monoketone of formula (III) can be prepared by acenaphthene quinone of formula (III-1) and aniline of formula (III-2) via a ketamine condensation reaction.

[0062]

[0063] Furthermore, the ketamine condensation reaction of acenaphthene with aniline can be carried out in an alcoholic organic solvent such as methanol, and the reaction can be carried out at room temperature for 3 to 12 hours (e.g., 5 to 8 hours). The molar ratio of acenaphthene to aniline can be 1 to 2:1, for example, 1.1 to 1.5:1.

[0064] A third aspect of the present invention provides an asymmetric binuclear ligand compound containing an heteroligand having the structure shown in formula (II):

[0065]

[0066] Among them, R 1 R 2 R 3 and R 4 Each is independently defined as described in any of the above technical solutions.

[0067] In some preferred embodiments, the ligand compound is selected from:

[0068]

[0069]

[0070] Specifically, the ligand compounds shown in the table above have the following group definitions:

[0071] L1:R 1 =H;R 2 =Me;R 3 = i Pr;R 4 =Me;

[0072] L2:R 1 =H;R 2 = i Pr;R 3 = i Pr;R 4 =Me;

[0073] L3:R 1 =H;R 2 = t Bu;R 3 = i Pr;R 4 =Me;

[0074] L4:R 1 =H;R 2 =OMe;R 3 = i Pr;R 4 =Me;

[0075] L5:R 1 =H;R 2 =OCF3;R 3 = i Pr;R 4 =Me;

[0076] L6:R 1 =H;R 2 =Cl;R 3 = i Pr;R 4 =Me;

[0077] L7;R 1 =H;R 2 =F;R 3 = i Pr;R 4 =Me;

[0078] L8:R 1 =H;R 2 =NO2; R 3 = i Pr;R 4 =Me.

[0079] A fourth aspect of the present invention provides a catalyst composition comprising a main catalyst and an optional co-catalyst, wherein the main catalyst is an asymmetric binuclear nickel complex containing heteroligands as described in any of the above-described technical solutions.

[0080] In some preferred embodiments, the cocatalyst is selected from one or more of the aluminoxane, alkylaluminum, and alkylaluminum chloride cocatalysts commonly used in the art.

[0081] In some preferred embodiments, the aluminum oxane cocatalyst is selected from one or more of methylaluminoxane (MAO) and triisobutylaluminum-modified methylaluminoxane (MMAO); the alkylaluminum cocatalyst is selected from trimethylaluminum (Me3Al), triethylaluminum (Et3Al), and triisobutylaluminum (Me3Al). i One or more of Bu3Al); the alkyl aluminum chloride cocatalyst is selected from one or more of diethylaluminum chloride (DEAC), dimethylaluminum chloride (Me2AlCl), triethylaluminum trichloride (EASC), and diethylaluminum chloride (EADC).

[0082] In some further preferred embodiments, when the cocatalyst is selected from methylaluminoxane (MAO), the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 1000 to 3000:1, for example, 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1 or any molar ratio range, more preferably 1500 to 2500:1, and most preferably 2000:1.

[0083] In some further preferred embodiments, when the cocatalyst is selected from triisobutylaluminum modified methylaluminoxane (MMAO), the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 1000 to 3000:1, for example, 1000:1, 1250:1, 1500:1, 1750:1, 2000:1, 2250:1, 2500:1, 2750:1, 3000:1 or any molar ratio range, more preferably 1500 to 2500:1, and most preferably 2000:1.

[0084] In some further preferred embodiments, when the co-catalyst is selected from dimethylaluminum chloride (Me2AlCl), the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 100 to 2000:1, for example, 100:1, 250:1, 500:1, 750:1, 1000:1, 1250:1, 1500:1, 1750:1, 2000:1 or any molar ratio range, more preferably 250 to 2000:1, and most preferably 500:1.

[0085] In some further preferred embodiments, when the cocatalyst is selected from trimethylaluminum (AlMe3), the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 100 to 2000:1, for example, 100:1, 250:1, 500:1, 750:1, 1000:1, 1250:1, 1500:1, 1750:1, 2000:1 or any molar ratio range, more preferably 250 to 2000:1, and most preferably 500:1.

[0086] The fifth aspect of the present invention provides the use of the asymmetric binuclear nickel complex containing heteroligands as described in any of the above-described technical solutions, or the catalyst composition as described in any of the above-described technical solutions, in the catalytic polymerization of olefins, especially in the catalytic polymerization of ethylene.

[0087] In some preferred embodiments, the ethylene polymerization is a homopolymerization of ethylene or a copolymerization of ethylene with an α-olefin.

[0088] In some more preferred embodiments, the α-olefin is a C3 to C20 α-olefin, such as a C3 to C12 α-olefin.

[0089] The sixth aspect of the present invention provides an olefin polymerization method, wherein the polymerization method uses the asymmetric binuclear nickel complex containing heteroligands as described in any of the above technical solutions, or the catalyst composition as described in any of the above technical solutions, as a catalyst.

[0090] In some preferred embodiments, the olefin polymerization is ethylene polymerization.

[0091] In some preferred embodiments, the ethylene polymerization is a homopolymerization of ethylene or a copolymerization of ethylene with an α-olefin.

[0092] In some further preferred embodiments, the α-olefin is a C3 to C20 α-olefin, such as a C3 to C12 α-olefin.

[0093] A seventh aspect of the present invention provides a method for preparing polyethylene, wherein the method uses the asymmetric binuclear nickel complex containing heteroligands as described in any of the above technical solutions, or the catalyst composition as described in any of the above technical solutions, as a catalyst, and ethylene is polymerized under its catalytic action to prepare polyethylene.

[0094] In some preferred embodiments, the polymerization reaction is carried out at a temperature of 20–80°C, for example, 20–60°C.

[0095] In some preferred embodiments, the polymerization reaction takes 5 to 100 minutes, for example, 20 to 50 minutes.

[0096] In some preferred embodiments, the polymerization reaction is carried out at a pressure of 0.3 to 20 atm, for example, 5 to 10 atm.

[0097] In some preferred embodiments, the polymerization reaction is carried out in a fourth organic solvent selected from one or more of toluene, xylene, dichloromethane, tetrahydrofuran, n-hexane, or cyclohexane.

[0098] In some preferred embodiments, the polyethylene is bimodal polyethylene.

[0099] In some preferred embodiments, the polymerization reaction is carried out in an ethylene atmosphere.

[0100] The technical solution provided by this invention has the following advantages:

[0101] 1. The binuclear nickel complex provided by this invention is an asymmetric binuclear N^N type nickel complex, which contains two types of active centers and a para-substituent (i.e., R) on the other side of the N-aryl group. 2 The nickel complex has a novel structure, simple preparation method, mild reaction conditions, short production cycle, simple and easy operation and control, and low cost, thus it has strong industrial applicability.

[0102] 2. The binuclear nickel complex provided by this invention has advantages such as high catalytic activity, low cost, and stable performance when used to catalyze olefin polymerization (especially ethylene polymerization). For example, in ethylene polymerization, at a polymerization temperature of 30°C, using Me₂AlCl as a co-catalyst, the highest activity of this binuclear nickel complex in catalyzing ethylene polymerization can reach 8.5 × 10⁻⁶. 6 g PE mol -1 (Ni)h -1 This method can produce branched polyethylene with a bimodal distribution and a large difference in molecular weight between the two parts.

[0103] 3. The binuclear nickel complex provided by this invention exhibits good thermal stability. When Me₂AlCl is used as a co-catalyst, the activity of this binuclear nickel complex in catalyzing ethylene polymerization remains as high as 4.1 × 10⁻⁶ under relatively high temperature conditions (60°C). 6 gPE mol -1 (Ni)h -1 It can also produce bimodal branched polyethylene. However, when the polymerization temperature is increased to 80℃, although the activity can still reach 2.9×10⁻⁶, the polymerization temperature still drops. 6 g PE mol -1 (Ni)h -1 However, the nickel active centers responsible for the low molecular weight portion no longer exhibit catalytic activity, and only the high molecular weight portion of polyethylene is ultimately obtained.

[0104] 4. When the polymerization conditions are changed, the weight-average molecular weight of the high molecular weight fraction of bimodal polyethylene prepared by the binuclear nickel complex or catalyst composition provided by this invention is between 5.8 and 22.1 × 10⁻⁶. 5 g mol -1 The molecular weight fluctuates between 1.9 and 3.5; while the low molecular weight fraction has a weight-average molecular weight of 580–5100 g / mol. -1 The molecular weight fluctuates between 1.3 and 2.3. This indicates that polymerization conditions such as polymerization temperature, co-catalyst dosage, and ethylene pressure have a strong regulatory effect on the molecular weight of polyethylene. It also reflects the significant differences in catalytic performance between the two types of active centers. The resulting bimodal polymerization product is a high-value-added polyethylene that is beneficial for improving the processing performance of high molecular weight polyethylene and has great potential for industrial applications.

[0105] 5. The bimodal polyethylene elastomer material prepared by the binuclear nickel complex or catalyst composition provided by the present invention has both molecular weight characteristics and high branching degree. Therefore, compared with polyethylene materials with only high molecular weight, it can achieve better mechanical properties. According to the fracture tensile test and elastic recovery test, the tensile strength of this type of material can reach 6.83 MPa, the elongation at break can reach 633.1%, and the elastic recovery rate is as high as 87%.

[0106] 6. The binuclear nickel complex provided by this invention has two catalytic active centers, and the molecular weight and branching degree of the two parts of the polymer can be effectively controlled by changing the electronic properties of the N-aryl para-substituent and the polymerization conditions.

[0107] 7. In the binuclear nickel complex catalyst system provided by the present invention, different active centers are adjacent to each other, so that the low molecular weight and ultra-high molecular weight polyethylene molecular chains grown on the active centers are closely intertwined with each other, achieving uniform mixing at the nanoscale, thereby realizing the uniformity of the final product. Attached Figure Description

[0108] Figure 1 This is a schematic diagram of the molecular structure obtained from the C3 single crystal in Example 11.

[0109] Figure 2 This is a schematic diagram of the molecular structure obtained from the C8 single crystal in Example 16.

[0110] Figure 3 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 25.

[0111] Figure 4 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 21.

[0112] Figure 5The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 32.

[0113] Figure 6 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 37.

[0114] Figure 7 The tensile properties of polyethylene obtained in Examples 21, 22d, 23, 24, 28 and 29 are shown in the figure (where PE-Ni1', 2', 6', 7' and 8' represent polyethylene prepared by using complexes C1, C2, C6, C7 and C8 as the main catalysts, respectively).

[0115] Figure 8 The figure shows the stress-strain recovery test results of the polyethylene obtained in Example 21.

[0116] Figure 9 The figure shows the stress-strain recovery test results of the polyethylene obtained in Example 22d.

[0117] Figure 10 The figure shows the stress-strain recovery test results of the polyethylene obtained in Example 22e. Detailed Implementation

[0118] the term

[0119] As used herein, "C1-Cn" includes C1-C2, C1-C3, ..., C1-Cn. For example, the "C1-C6" group refers to a moiety containing 1 to 6 carbon atoms, that is, a group containing 1, 2, 3, 4, 5, or 6 carbon atoms. Therefore, for example, "C1-C4 alkyl" refers to an alkyl group containing 1 to 4 carbon atoms.

[0120] The term "alkyl" as used alone or in combination herein refers to a saturated aliphatic hydrocarbon that is optionally substituted with a straight chain or optionally substituted with a branched chain. "alkyl" as used herein preferably has 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, and hexyl, as well as longer alkyl groups such as heptyl and octyl. Alkyl groups in this document also include cases where no numerical range is specified.

[0121] The term “alkyl” as used in this article refers to an alkyl group linked to other groups, such as an alkyl group in an alkoxy group, and is defined the same as when used alone.

[0122] The term "alkoxy" as used alone or in combination herein refers to an alkyl ether group, denoted as "alkyl-O-". Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

[0123] The term “halogenated” as used alone or in combination herein refers to the substitution of one or more hydrogen atoms (including all hydrogen atoms) in a group by one or more halogens, the definition of which is the same as when used alone.

[0124] The term "cycloalkyl" as used alone or in combination herein refers to a non-aromatic saturated carbocyclic ring, which may include a single-carbon ring (having one ring), a double-carbon ring (having two rings), or a multi-carbon ring (having more than two rings), and the rings may be bridged or spirocyclic. A cycloalkyl group may have 3 to 10 cyclic carbon atoms, for example, 3 to 6 cyclic carbon atoms. Non-limiting examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0125] The term "aryl" as used alone or in combination herein refers to an optionally substituted aromatic hydrocarbon group having 6 to 14, such as 6 to 12 or 6 to 10 cyclic carbon atoms, which can be monocyclic, bicyclic, or more cyclic aryl. A bicyclic or more cyclic aryl group can be a monocyclic aryl group fused with other independent rings, such as alicyclic or aromatic rings. Non-limiting examples of monocyclic aryl groups include phenyl; non-limiting examples of bicyclic aryl groups include naphthyl; non-limiting examples of polycyclic aryl groups include phenanthryl, anthracene, fluorenyl, and azulel.

[0126] The term “halogen” as used alone or in combination in this article refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0127] The technical solution of the present invention will be further described in detail below with reference to specific embodiments.

[0128] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0129] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0130] Unless otherwise specified, all concentrations in the following examples are molar concentrations.

[0131] In the following ethylene polymerization examples, the molecular weight and molecular weight distribution of the polymers obtained were determined using conventional high-temperature GPC methods, the melting points were determined using conventional DSC methods, and the polymerization activity of the polymers was calculated using the following formula: Polymer activity = Polymer yield / (Catalyst dosage · Polymerization time). The degree of branching was determined by dissolving 50 mg of the corresponding polymer in 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 curve data at room temperature when the sample fractured. Elastic recovery rate (SR) was obtained from DMA curve data measured at room temperature.

[0132] The structures of all the synthesized complexes described below were confirmed by infrared and elemental analysis.

[0133] The synthetic routes for the binuclear nickel complexes in the following examples are as follows:

[0134]

[0135] Example 1

[0136] Preparation of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methylphenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine

[0137] A catalytic amount of p-toluenesulfonic acid (0.038 g, 20 mol%) was added to a dry toluene solution (30 mL) of 2-(2,6-bis(diphenylmethyl)-4-methylbenzyl)acenaphthene (0.60 g, 1.00 mmol) and 3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4,4'-diamine (0.46 g, 1.30 mmol), and the mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by alkaline alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 25:1) as the eluent. The eluent fraction was detected by thin-layer silica gel plate analysis, and the fourth fraction was collected. The solvent was removed to give an orange powder product (0.19 g, yield 20%).

[0138] The structural verification data is as follows:

[0139] 1H NMR (400MHz, CDCl3, TMS): δ7.67(d,J=8.0Hz,1H),7.50(d,J=8.0Hz,1H),7.48(s,2H),7.41(s,2H ),7.28-7.19(m,7H),7.13(d,J=6.0Hz,4H),6.95-6.88(m,5H),6.81(s,2H),6.58(t,J=8.0Hz,5H ),6.39(t,J=8.0Hz,2H),5.92(d,J=8.0Hz,1H),5.65(s,2H),3.83(s,2H),3.23-3.19(m,2H),3.0 6-3.03(m,2H),2.29(s,3H),1.41(d,J=4.0Hz,12H),1.34(d,J=8.0Hz,6H),1.07(d,J=8.0Hz,6H).

[0140] 13 C NMR (CDCl3, 100MHz): δ163.9,162.4,147.1,145.9,143.7,141.8,140.1,1397,138.2,136.0,133.0,132.7,132.5,132.0,129.9,129.8,129.7 ,129.0,128.8,128.6,128.2,127.9,127.1,127.0,126.2,125.6,124.4 ,123.2,122.0,121.9,121.5,52.3,28.8,28.4,24.4,24.0,22.7,21.7.

[0141] FT-IR (cm) -1 ):3472(w),3391(w),3058(w),3029(w),2959(m),2923(w),2868(w),1664(ν(C=N),m),1646(ν(C=N),m),1 597(m),1494(m),1436(m),1342(m),1259(s),1085(m),1013(s),925(m),866(m),792(s),744(m),698(m).

[0142] Elemental analysis: C 69 H 67 Theoretical values ​​for N3 (938.32): C, 88.32; H, 7.20; N, 4.48. Experimental values: C, 88.09; H, 7.45; N, 4.13.

[0143] The preparation of (1E,2E)-N1-(2,6-bis(diphenylmethyl)-4-methylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylpyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine[L1], wherein R 1 For hydrogen, R 2 For methyl, R 3 It is isopropyl, R 4 It is a methyl group.

[0144] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methylphenyl)imine)acenaphthyl-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.188 g, 0.20 mmol), and the mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L1 (0.0860 g, yield 41%).

[0145] The structural verification data is as follows:

[0146] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=4.0Hz,1H),8.41(d,J=8.0Hz,1H),7.85(t,J=7.8Hz,1H),7.69(d,J=8.0Hz,1 H),7.57-7.51(m,5H),7.42(t,J=6.0Hz,1H),7.29-7.18(m,7H),7.13(d,J=8.0Hz,4H),6.96-6.91(m,5H),6.82(s, 2H),6.66(d,J=8.0Hz,1H),6.58(t,J=6.0Hz,4H),6.40(t,J=8.0Hz,2H),5.94(d,J=4.0Hz,1H),5.66(s,2H),3.26- 3.22(m,2H),2.88-2.84(m,2H),2.30(s,6H),1.37(d,J=4.0Hz,6H),1.28(t,J=8.0Hz,12H),1.10(d,J=4.0Hz,6H).

[0147] 13 C NMR (CDCl3, 100MHz): δ167.4,163.9,162.5,156.7,148.8,147.1,146.3,145. 9,143.8,141.9,140.1,137.8,136.9,136.7,136.4,136.1,132.8,132.5,129. 9,129.7,129.0,128.7,128.2,127.9,127.0,126.2,125.6,125.0,124.4,123.2,122.1,121.7,121.6,52.3,52.5,28.8,28.7,24.4,24.0,23.5,23.0,17.6.

[0148] FT-IR (cm) -1 ):3057(w),3029(w),2959(m),2935(w),2868(w),1647(ν(C=N),m),1593

[0149] (m),1567(m),1493(m),1459(m),1438(m),1363(m),1323(w),1300(w),11 89(m),1098(m),1035(m),925(w),867(m),811(m),781(m),43(m),698(s).

[0150] Elemental analysis: C 76 H 72 Theoretical values ​​for N4 (1041.44): C, 87.65; H, 6.97; N, 5.38. Experimental values: C, 87.42; H, 7.05; N, 5.42.

[0151] Example 2

[0152] The preparation of (1E,2E)-N1-(2,6-bis(diphenylmethyl)-4-isopropylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine[L2], wherein R 1 For hydrogen, R 2 It is isopropyl, R 3 It is isopropyl, R 4 It is a methyl group.

[0153] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-isopropylphenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.194 g, 0.20 mmol, prepared according to the method of Example 1 using different acenaphthenicotinamide ketones). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L2 (0.0820 g, yield 38%).

[0154] The structural verification data is as follows:

[0155] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=8.0Hz,1H),8.41(d,J=8.0Hz,1H),7.85(t,J=8.0Hz,1H),7.68(d,J=8.0Hz,1H), 7.57-7.49(m,5H),7.44-7.40(m,1H),7.28-7.17(m,7H),7.14-7.10(m,4H),6.96-6.91(m,4H),6.89-6.82(m,3H),6.6 6(d,J=8.0Hz,1H),6.60-6.56(m,4H),6.42-6.37(m,2H),5.82(d,J=8.0Hz,1H),5.68(s,2H),3.27-3.20(m,2H),2.89- 2.79(m,3H),2.30(s,3H),1.38(d,J=8.0Hz,6H),1.28(t,J=8.0Hz,12H),1.16(d,J=8.0Hz,6H),1.11(d,J=8.0Hz,6H).

[0156] 13C NMR (CDCl3, 100MHz): δ167.4,163.9,162.4,156.7,148.8,146.4,145.9,143.9,14 1.9,140.1,139.2,138.6,138.5,137.8,136.9,136.7,136.4,136.1,135.5,132.2, 129.9,129.7,128.9,128.7,128.2,127.9,127.0,126.4,126.1,125.6,125.0,124.4,122.1,121.7,121.6,52.4,33.7,28.8,28.7,24.4,24.3,23.9,23.5,23.0,17.6.

[0157] FT-IR (cm) -1 ):3058(w),3032(w),2959(m),2935(w),2868(w),1649(ν(C=N),m),1593

[0158] (m),1567(m),1493(m),1461(m),1438(m),1363(m),1324(w),1265(w),119 1(m),1103(m),1037(m),926(w),870(m),822(m),782(m),738(m),698(s).

[0159] Elemental analysis: C 78 H 76 Theoretical values ​​for N4 (1069.49): C, 87.60; H, 7.16; N, 5.24. Experimental values: C, 87.46; H, 7.36; N, 5.20.

[0160] Example 3

[0161] The preparation of (1E,2E)-N1-(2,6-bis(diphenylmethyl)-4-tert-butylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine[L3], wherein R 1 For hydrogen, R 2 For tert-butyl, R 3 It is isopropyl, R 4 It is a methyl group.

[0162] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-tert-butylphenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.196 g, 0.20 mmol, prepared according to the method of Example 1 using a different acenaphthenicotinamide ketone). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L3 (0.0980 g, yield 45%).

[0163] The structural verification data is as follows:

[0164] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=4.0Hz,1H),8.41(d,J=8.0Hz,1H),7.85(t,J=8.0Hz,1H),7.68(d,J=8.0Hz,1H),7.57(s,2H), 7.53(s,2H),7.50(d,J=8.0Hz,1H),7.42(t,J=8.0Hz,1H),7.27-7.16(m,7H),7.11(d,J=8.0Hz,4H),7.02(s,2H),6.93(d,J=8.0Hz,4 H),6.87(t,J=8.0Hz,1H),6.66(d,J=8.0Hz,1H),6.58(t,J=8.0Hz,4H),6.39(t,J=8.0Hz,2H),5.79(d,J=4.0Hz,1H),5.68(s,2H),3 .25-3.22(m,2H),2.87-2.84(m,2H),2.30(s,3H),1.38(d,J=4.0Hz,6H),1.28(t,J=8.0Hz,12H),1.20(s,9H),1.11(d,J=8.0Hz,6H).

[0165] 13C NMR (CDCl3, 100MHz): δ167.4,162.3,156.7,148.8,147.1,146.2,145.9,14 3.9,142.0,140.1,137.8,136.9,136.7,136.4,136.1,131.8,129.9,129.8, 129.7,128.9,128.7,128.1,127.9,127.1,126.1,125.6,125.4,124.4,123.2,122.1,121.7,52.5,34.6,31.6,28.8,28.7,24.4,23.9,23.5,23.0,17.6.

[0166] FT-IR (cm) -1 ):3057(w),3024(w),2958(m),2868(w),1648(ν(C=N),m),1593(m),1562

[0167] (m),1493(m),1460(m),1437(m),1386(w),1363(m),1324(w),1267(w),119 0(m),1104(m),1037(m),924(w),869(m),823(m),780(m),736(m),698(s).

[0168] Elemental analysis: C 79 H 78 Theoretical values ​​of N4 (1083.52): C, 87.57; H, 7.26; N, 5.17. Experimental values: C, 87.25; H, 7.33; N, 5.36.

[0169] Example 4

[0170] The preparation of (1E,2E)-N1-(2,6-bis(diphenylmethyl)-4-methoxyphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine[L4], wherein R 1 For hydrogen, R 2 It is a methoxy group, R 3 It is isopropyl, R 4 It is a methyl group.

[0171] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methoxyphenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.190 g, 0.20 mmol, prepared according to Example 1 using a different acenaphthenicotinamide ketone). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L4 (0.0620 g, yield 29%).

[0172] The structural verification data is as follows:

[0173] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=4.0Hz,1H),8.41(d,J=8.0Hz,1H),7.83(t,J=8.0Hz,1H),7.70(d,J=8 .0Hz,1H),7.56-7.53(m,5H),7.42(t,J=6.0Hz,1H),7.26-7.13(m,11H),6.96-6.91(m,5H),6.66(d,J=8.0Hz ,1H),6.61-6.57(m,6H),6.41(t,J=8.0Hz,2H),6.00(d,J=8.0Hz,1H),5.67(s,2H),3.66(s,3H),3.26-3.19( m,2H),2.89-2.82(m,2H),2.30(s,3H),1.37(d,J=8.0Hz,6H),1.28(t,J=6.0Hz,12H),1.10(d,J=8.0Hz,6H).

[0174] 13C NMR (CDCl3, 100MHz): δ167.4,164.5,162.4,155.9,148.8,143.4,141.6,140.2,138.4,137.8,136.4,136.1,133.9,129.9,1 29.7,128.7,128.6,128.3,128.0,126.4,125.7,124.4,122.1,121.7,114.1,55.4,52.4,288,24.4,24.0,23.5,23.0,17.5.

[0175] FT-IR (cm) -1 ):3057(w),3032(w),2959(m),2932(m),2830(w),1647(ν(C=N),m),1594(m),1562(ν(C=N),m),1493(m),1461(m), 1436(m),1362(w),1321(w),1190(m),1098(s),1052(m),957(w),926(m),869(m),813(m),781(m),743(m),699(s).

[0176] Elemental analysis: C 76 H 72 Theoretical values ​​for N4O (1057.44): C, 86.33; H, 6.86; N, 5.30. Experimental values: C, 86.01; H, 6.95; N, 5.42.

[0177] Example 5

[0178] The preparation of (1E,2E)-N1-(2,6-bis(diphenylmethyl)-4-trifluoromethoxyphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine [L5], wherein R 1 For hydrogen, R 2 It is trifluoromethoxy, R 3 It is isopropyl, R 4 It is a methyl group.

[0179] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-trifluoromethoxyphenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.200 g, 0.20 mmol, prepared according to the method of Example 1 using a different acenaphthenicotinamide ketone). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by alkaline alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L5 (0.0840 g, yield 38%).

[0180] The structural verification data is as follows:

[0181] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=8.0Hz,1H),8.41(d,J=8.0Hz,1H),7.85(t,J=8.0Hz,1H),7.71(d,J=8.0Hz ,1H),7.58-7.53(m,5H),7.42(dd,J=8.0Hz,1H),7.31-7.20(m,7H),7.10(d,J=8.0Hz,4H),6.90(t,J=4.0Hz,7H) ,6.68(d,J=8.0Hz,2H),6.59(t,J=8.0Hz,4H),6.41(t,J=8.0Hz,2H),5.85(d,J=8.0Hz,1H),5.69(s,2H),3.24-3 .21(m,2H),2.88-2.84(m,2H),2.30(s,3H),1.38(d,J=8.0Hz,6H),1.28(t,J=8.0Hz,12H),1.12(d,J=4.0Hz,6H).

[0182] 13C NMR (CDCl3, 100MHz): δ167.4,164.4,161.9,156.7,148.8,148.0,146.1,146 .0,142.8,140.8,138.0,136.7,136.5,136.0,134.6,129.8,129.6,128.9,1 28.7,128.4,128.2,127.3,127.1,126.7,126.0,125.0,124.3,124.1,123.4,122.2,121.7,121.6,121.3,52.3,28.9,28.7,24.4,23.9,23.5,23.0,17.6.

[0183] 19 F NMR (470MHz, CDCl3): δ-58.13,-59.19.

[0184] FT-IR (cm) -1 ):3059(w),3029(w),2959(m),2935(w),2869(w),1652(ν(C=N),m),1592

[0185] (m),1565(w),1494(m),1460(m),1438(m),1364(w),1359(s),1217(m),11 88(m),1162(m),1102(m),925(m),870(m),826(m),780(m),29(m),698(s).

[0186] Elemental analysis: C 76 H 69 Theoretical values ​​for F3N4O(1111.41): C, 82.13; H, 6.26; N, 5.04. Experimental values: C, 81.79; H, 6.33; N, 5.23.

[0187] Example 6

[0188] The preparation of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-chlorophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine[L6], wherein R 1 For hydrogen, R 2 For chlorine, R 3 It is isopropyl, R 4 It is a methyl group.

[0189] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-chlorophenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.196 g, 0.20 mmol, prepared according to the method of Example 1 using different acenaphthenicotinamide ketones). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L6 (0.0980 g, yield 50%).

[0190] The structural verification data is as follows:

[0191] 1 H NMR (400MHz, CDCl3, TMS): δ8.72(d,J=4.0Hz,1H),8.41(d,J=8.0Hz,1H),7.85(t,J=8.0Hz,1H),7.71(d,J=8.0Hz,1 H),7.57-7.53(m,5H),7.43(t,J=4.0Hz,1H),7.31-7.10(m,7H),7.11(d,J=8.0Hz,4H),7.01(s,2H),6.97-6.92(m, 5H),6.67(d,J=8.0Hz,1H),6.60(t,J=8.0Hz,4H),6.41(t,J=8.0Hz,2H),5.97(d,J=8.0Hz,1H),5.66(s,2H),3.23- 3.20(m,2H),2.88-2.84(m,2H),2.30(s,3H),1.38(d,J=4.0Hz,6H),1.28(t,J=8.0Hz,12H),1.11(d,J=4.0Hz,6H).

[0192] 13C NMR (CDCl3, 100MHz): δ167.4,164.2,162.2,156.7,148.8,148.0,146.1,142.8,141.0,138.0,136.7,136.5,136.0,134.8,129.8,129.6,1 29.1,128.9,128.4,128.3,128.1,127.3,126.6,126.0,124.4,123.4 ,122.2,121.7,121.6,52.3,28.9,28.7,24.4,23.9,23.5,23.0,17.6.

[0193] FT-IR (cm) -1 ):3062(w),3029(w),2960(m),2928(w),2871(w),1648(ν(C=N),m),1593

[0194] (m),1569(m),1493(m),1460(m),1435(s),1363(m),1324(w),1276(w),1188(m) ,1102(m),1076(m),1040(m),894(w),869(m),827(m),780(m),738(m),697(s).

[0195] Elemental analysis: C 75 H 69 ClN4 (1061.86) Theoretical values: C, 84.84; H, 6.55; N, 5.28. Experimental values: C, 84.65; H, 6.89; N, 5.32.

[0196] Example 7

[0197] The preparation of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-fluorophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine [L7], wherein R 1 For hydrogen, R 2 It is fluorine, R 3 It is isopropyl, R 4 It is a methyl group.

[0198] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-fluorophenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.188 g, 0.20 mmol, prepared according to the method of Example 1 using different acenaphthenicotinamide ketones). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L7 (0.0840 g, yield 40%).

[0199] The structural verification data is as follows:

[0200] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=8.0Hz,1H),8.41(d,J=12.0Hz,1H),7.85(t,J=8.0Hz,1H),7.71(d,J=8.0Hz,1H) ,7.57-7.53(m,5H),7.42(dd,J=4.0Hz,1H),7.38-7.22(m,7H),7.13(d,J=12.0Hz,4H),6.94(t,J=6.0Hz,4H),6.76(d,J =8.0Hz,2H),6.67(d,J=8.0Hz,1H),6.60(t,J=8.0Hz,4H),6.41(t,J=7.4Hz,2H),5.95(d,J=8.0Hz,1H),5.67(s,2H),3 .22-3.19(m,2H),2.88-2.84(m,2H),2.30(s,3H),1.38(d,J=8.0Hz,6H),1.28(t,J=8.0Hz,12H),1.11(d,J=8.0Hz,6H).

[0201] 13C NMR (CDCl3, 100MHz): δ167.4,164.6,162.2,156.7,148.8,146.2,145.9,1 42.9,141.0,137.9,136.7,136.5,136.1,134.8,129.8,129.6,128.9,128. 4,128.3,128.1,127.2,127.0,126.6,125.9,125.0,124.4,123.3,122.2,1 21.7,121.6,115.5,115.2,52.3,28.8,28.7,24.4,23.9,23.5,23.0,17.6. 19 F NMR (470MHz, CDCl3): δ-119.21.

[0202] FT-IR (cm) -1 ):3057(w),3032(w),2957(m),2928(w),1646(ν(C=N),m),1592(m),1562

[0203] (m),1493(m),1459(m),1438(s),1362(m),1324(w),1300(w),1189(m),110 2(m),1027(w),1040(m),994(w),927(m),868(m),781(m),743(m),699(s).

[0204] Elemental analysis: C 75 H 69 FN4 (1045.40) theoretical values: C, 86.17; H, 6.65; N, 5.36. Experimental values: C, 85.96; H, 6.85; N, 5.37.

[0205] Example 8

[0206] The preparation of (1E,2E)-N1-(2,6-bis(diphenylmethyl)-4-nitrophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine [L8], wherein R 1 For hydrogen, R 2 It is nitro, R 3 It is isopropyl, R 4 It is a methyl group.

[0207] A catalyst amount of p-toluenesulfonic acid (0.00760 g, 20 mol%) was added to a dry toluene solution (30 mL) of acetylpyridine (0.122 g, 1.00 mmol) and 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-nitrophenyl)imine)acenaphthenico-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.192 g, 0.20 mmol, prepared according to the method of Example 1 using a different acenaphthenicotinamide ketone). The mixture was heated to reflux for 8 h. After the reaction was complete (as verified by TLC), the reaction mixture was cooled to room temperature. The solvent toluene was removed, and the residue was purified by basic alumina column chromatography using a mixture of petroleum ether / ethyl acetate (v / v = 50:1) as the eluent. The elution fraction was detected by thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to obtain orange powder L8 (0.120 g, yield 58%).

[0208] The structural verification data is as follows:

[0209] 1 H NMR (400MHz, CDCl3, TMS): δ8.71(d,J=4.0Hz,2H),8.41(d,J=8.0Hz,1H),7.95(s,2H),7.85(t,J=10.0Hz,1H),7.74(d,J= 8.0Hz,1H),7.59-7.57(m,3H),7.57(s,1H),7.53(s,2H),7.44-7.41(m,1H),7.33-7.25(m,7H),7.12(d,J=8.0Hz,4H),6. 96-6.90(m,5H),6.71(d,J=4.0Hz,1H),6.60(t,J=8.0Hz,4H),6.42(t,J=8.0Hz,2H),5.86(d,J=4.0Hz,1H),5.73(s,2H), 3.22-3.20(m,2H),2.88-2.85(m,2H),2.30(s,3H),1.39(d,J=4.0Hz,6H),1.28(d,J=6.0Hz,12H),1.13(d,J=4.0Hz,6H).

[0210] 13C NMR(CDCl3,100MHz): δ167.4,163.6,162.0,156.6,155.3,148.8,146.0, 145.9,144.4,142.1,140.3,138.3,136.7,136.5,136.0,134.6,129.8,1 29.5,129.1,128.9,128.7,128.4,128.0,127.0,126.3,125.0,123.8,12 3.6,122.2,121.7,121.6,52.4,29.0,28.7,24.4,23.9,23.4,23.0,17.6.

[0211] FT-IR (cm) -1 ):3058(w),3029(w),2960(m),2928(w),2867(w),1673(ν(C=N),m),1643

[0212] (ν(C=N),m),1588(m),1515(m),1494(m),1458(m),1432(m),1363(m),1332(s),124 4(m),1192(m),1103(m),1036(m),918(w),870(w),830(w),781(m),737(m),698(s).

[0213] Elemental analysis: C 75 H 69 Theoretical values ​​for N5O2 (1072.41): C, 84.00; H, 6.49; N, 6.53. Experimental values: C, 83.75; H, 6.71; N, 6.27.

[0214] Example 9

[0215] Prepare the nickel bromide (II) [complex C1] of formula (I) shown, [(1E,2E)-N1-(2,6-di(diphenylmethyl)-4-methylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylenepyridinyl)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine], wherein R 1 For hydrogen, R 2 For methyl, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0216] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-methylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.052 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.055 g), with a yield of 75%.

[0217] The structural verification data is as follows:

[0218] FT-IR (cm) -1 ):3353(br,m),3057(w),3032(w),2963(w),2932(w),2867(m),1645(ν(C=N),m),1620(ν(C=N),m),1597(m),1494(m),144 1(m),1368(w),1322(w),1295(w),1261(w),1187(w),1128(w),1028(w),921(w),870(w),828(w),773(m),745(w),700(s).

[0219] Elemental analysis: C 76 H 74 Theoretical values ​​for Br4N4Ni2O (1496.46): C, 61.00; H, 4.98; N, 3.74. Experimental values: C, 60.81; H, 5.13; N, 3.83.

[0220] Example 10

[0221] Prepare the [(1E,2E)-N1-(2,6-di(diphenylmethyl)-4-isopropylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine]nickel bromide (II) [complex C2] as shown in formula (I), wherein R 1 For hydrogen, R 2 It is isopropyl, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0222] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-isopropylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.048 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to the solution to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.053 g), with a yield of 71%.

[0223] The structural verification data is as follows:

[0224] FT-IR (cm) -1 ):3337(br,w),3055(w),2955(m),2928(w),1647(ν(C=N),m),1620(ν(C=N),

[0225] m),1592(m),1493(m),1443(m),1364(w),1321(w),1292(m),1260(w),1183(m),1126(m),947(m),872(m),827(m),772(m),701(s).

[0226] Elemental analysis: C 78 H 78 Theoretical values ​​for Br4N4Ni2O (1524.51): C, 61.45; H, 5.16; N, 3.68. Experimental values: C, 61.31; H, 5.23; N, 3.83.

[0227] Example 11

[0228] Prepare the [(1E,2E)-N1-(2,6-di(diphenylmethyl)-4-tert-butylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine]nickel bromide (II) [complex C3] as shown in formula (I), wherein R 1 For hydrogen, R 2 For tert-butyl, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0229] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-tert-butylphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.049 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to the solution to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.052 g), with a yield of 69%.

[0230] The structural verification data is as follows:

[0231] FT-IR (cm) -1 ):3360(br,w),3057(w),2958(w),2937(w),2864(m),1643(ν(C=N),m),

[0232] 1619(ν(C=N),m),1589(m),1493(m),1441(m),1366(w),1320(w),1290(w),1260( w),1184(m),1124(w),1028(w),944(w),874(w),827(w),774(m),744(w),701(s).

[0233] Elemental analysis: C 79 H 80 Theoretical values ​​for Br4N4Ni2O (1538.54): C, 61.67; H, 5.24; N, 3.64. Experimental values: C, 61.41; H, 5.42; N, 3.73.

[0234] Hexane was diffused into a dichloromethane solution of the complex using a slow diffusion method at room temperature, resulting in the growth of C3 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 and a distorted triangular bipyramidal geometry around the two nickel centers.

[0235] Example 12

[0236] Prepare the [(1E,2E)-N1-(2,6-di(diphenylmethyl)-4-methoxyphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine]nickel bromide (II) [complex C4] as shown in formula (I), wherein R 1 For hydrogen, R 2 It is a methoxy group, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0237] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-methoxyphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.048 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to the solution to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.059 g), with a yield of 79%.

[0238] The structural verification data is as follows:

[0239] FT-IR (cm) -1 ):3330(br,w),3330(w),3057(w),2958(m),2925(w),2833(w),1649(ν(C=N),m),1620(ν(C=N),m),1592(m),1491(m),1456(m) ,1440(w),1365(w),1319(m),1293(m),1187(m),1131(m),1050(w),1026(w),949(m),871(m),828(m),773(m),743(m),700(s).

[0240] Elemental analysis: C 76 H 74 Theoretical values ​​for Br4N4Ni2O2 (1512.46): C, 60.35; H, 4.93; N, 3.70. Experimental values: C, 60.12; H, 4.99; N, 3.71.

[0241] Example 13

[0242] Prepare the nickel bromide (II) [complex C5] of formula (I) shown in formula (I), wherein R 1 For hydrogen, R 2 It is trifluoromethoxy, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0243] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.1 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-trifluoromethoxyphenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.050 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to the solution to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a black solid (0.058 g), with a yield of 75%.

[0244] FT-IR (cm) -1 ):3330(br,m),3065(w),2956(w),2928(w),1646(ν(C=N),m),1624(ν(C=N),

[0245] m),1590(m),1493(m),1440(m),1367(w),1321(w),1292(w),1252(s),1217(s),1162(s),1025(w),948(w),871(w),828(w),773(m),702(s).

[0246] Elemental analysis: C 76 H 71 Theoretical values ​​for Br4F3N4Ni2O2 (1566.43): C, 58.28; H, 4.57; N, 3.58. Experimental values: C, 58.19; H, 4.65; N, 3.59.

[0247] Example 14

[0248] Prepare the [(1E,2E)-N1-(2,6-di(diphenylmethyl)-4-chlorophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridinyl)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine]nickel bromide (II) [complex C6] as shown in formula (I), wherein R 1 For hydrogen, R 2 For chlorine, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0249] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-chlorophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridinyl)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.048 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.055 g), with a yield of 73%.

[0250] FT-IR (cm) -1 ):3379(br,w),3062(w),3032(m),2961(m),2930(w),2866(w),1647(ν(C=N),m),1620(ν(C=N),m),1600(m),1494(m) ,1580(m),1491(m),1434(m),1340(m),1291(w),1182(m),1075(m),894(m),870(m),828(m),770(m),740(w),700(s).

[0251] Elemental analysis: C 75 H 71 Theoretical values ​​for Br4ClN4Ni2O (1516.87): C, 59.39; H, 4.72; N, 3.69. Experimental values: C, 59.12; H, 4.97; N, 3.75.

[0252] Example 15

[0253] Prepare the nickel bromide (II) [complex C7] of formula (I) shown in formula (I), wherein R 1 For hydrogen, R 2 It is fluorine, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0254] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-fluorophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.047 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to the solution to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.057 g), with a yield of 77%.

[0255] FT-IR (cm) -1 ):3345(br,w),3059(w),2960(w),2925(w),2863(m),1645(ν(C=N),m),

[0256] 1624(ν(C=N),m),1590(m),1492(m),1438(m),1366(w),1319(w),1293(w),1259( w),1181(m),1116(w),1027(w),999(w),869(w),828(w),772(m),745(w),700(s).

[0257] Elemental analysis: C 75 H 71 Theoretical values ​​for Br4FN4Ni2O(1500.42): C, 60.04; H, 4.77; N, 3.73. Experimental values: C, 59.85; H, 4.89; N, 3.81.

[0258] Example 16

[0259] Prepare the nickel bromide (II) [complex C8] of formula (I) shown in formula (I), wherein R 1 For hydrogen, R 2 It is nitro, R 3 It is isopropyl, R 4 X is methyl, and bromine is bromine.

[0260] Under nitrogen protection, 2 equivalents of (DME)NiBr2 (0.031 g, 0.10 mmol) were added to a solution of (1E,2E)-N1-(2,6-di(diphenylmethyl)-4-nitrophenyl)-N2-3,3',5,5'-tetraisopropyl-4'-(((E)-1-(2-ethylidenepyridine)imine)-[1,1'-biphenyl]-4-acenaphthyl-1,2-diimine (0.048 g, 0.050 mmol) in dichloromethane (10 mL). After stirring the mixture at room temperature for 12 h, most of the dichloromethane was removed under reduced pressure, and the solution was concentrated to approximately 2 mL. Diethyl ether (20 mL) was added to the solution to recrystallize the product, forming a precipitate. The collected solid was washed with 3 × 10 mL of diethyl ether and dried under vacuum to give a brown solid (0.050 g), with a yield of 79%.

[0261] FT-IR (cm) -1 ):3343(br,m),3060(w),3031(w),2961(w),2932(w),2867(m),1648(ν(C=N),m),1624(ν(C=N),m),1593(m),1524(m),1494(m) ,1440(m),1326(w),1293(w),1259(w),1185(m),1103(w),1028(w),950(w),917(w),871(w),824(w),772(m),741(w),700(s).

[0262] Elemental analysis: C 75 H 71 Theoretical values ​​for Br4N5Ni2O3 (1527.43): C, 58.98; H, 4.69; N, 4.59. Experimental values: C, 58.82; H, 4.84; N, 4.63.

[0263] Hexane was diffused into a dichloromethane solution of the complex using a slow diffusion method at room temperature, resulting in the growth of C8 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 has an asymmetric structure, and the coordinating atoms exhibit a distorted tetrahedral geometry and a distorted triangular bipyramidal geometry around the two nickel centers.

[0264] Example 17

[0265] Ethylene polymerization under pressure using C8 complex and MAO co-catalyst:

[0266] 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 one backfilling with ethylene. Under an ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C8 (0.5 μmol), 1.4 mL of co-catalyst MAO (1.46 mol / L, toluene solution), and 50 mL of toluene were sequentially added to the 250 mL stainless steel autoclave, at which point the Al / Ni ratio was 2000:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30 °C, ethylene was introduced into the reactor, and the polymerization reaction began. An ethylene pressure of 10 atm was maintained at 30 °C, and stirring was continued for 30 min. After the reaction was completed, the ethylene supply was stopped, and the reactor was vented after cooling. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0267] Polymerization activity: 4.0 × 10 6 g·mol -1 (Ni)·h -1 Polymer T m =73.2,111.8℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =4.4×10 5 g·mol -1 PDI1 = 1.8; M w2 =0.024×10 5 g·mol -1 PDI2 = 1.7 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0268] Example 18

[0269] Ethylene polymerization under pressure using C8 complex and MMAO co-catalyst:

[0270] 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 one backfilling with ethylene. Under an ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C8 (0.5 μmol), 1.1 mL of co-catalyst MMAO (1.93 mol / L, heptane solution), and 50 mL of toluene were sequentially added to the 250 mL stainless steel autoclave, at which point the Al / Ni ratio was 2000:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30 °C, ethylene was introduced into the reactor, and the polymerization reaction began. An ethylene pressure of 10 atm was maintained at 30 °C, and stirring was continued for 30 min. After the reaction was complete, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0271] Polymerization activity: 2.8 × 10 6 g·mol -1 (Ni)·h -1 Polymer T m =86.7,116.5℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =8.1×10 5 g·mol -1 PDI1 = 2.0; M w2 =0.030×10 5 g·mol -1 PDI2 = 1.9 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0272] Example 19

[0273] Ethylene polymerization under pressure using C8 complex and Me2AlCl as co-catalysts:

[0274] 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 one backfilling with ethylene. Under an ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C8 (0.5 μmol), 0.5 mL of co-catalyst Me2AlCl (1.00 mol / L, toluene solution), and 50 mL of toluene were sequentially added to the 250 mL stainless steel autoclave, at which point the Al / Ni ratio was 500:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30 °C, ethylene was introduced into the reactor, and the polymerization reaction began. An ethylene pressure of 10 atm was maintained at 30 °C, and stirring was continued for 30 min. After the reaction was completed, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0275] Polymerization activity: 5.9 × 10 6 g·mol -1 (Ni)·h -1 Polymer T m =57.4,113.0℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =4.6×10 5 g·mol -1 PDI1 = 2.0; M w2 =0.014×10 5 g·mol -1 PDI2 = 1.6 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0276] Example 20

[0277] Ethylene polymerization under pressure using C8 complex and AlMe3 co-catalyst:

[0278] 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 one backfilling with ethylene. Under an ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C8 (0.5 μmol), 0.25 mL of co-catalyst AlMe3 (2.00 mol / L, n-hexane solution), and 50 mL of toluene were sequentially added to the 250 mL stainless steel autoclave, at which point the Al / Ni ratio was 500:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30 °C, ethylene was introduced into the reactor, and the polymerization reaction began. An ethylene pressure of 10 atm was maintained at 30 °C, and stirring was continued for 30 min. After the reaction was completed, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0279] Polymerization activity: 4.6 × 10 6 g·mol -1 (Ni)·h -1 Polymer T m =89.3,118.2℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =11.3×10 5 g·mol -1 PDI1 = 1.8; M w2 =0.042×10 5 g·mol -1 PDI2 = 2.5 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0280] Example 21

[0281] Ethylene polymerization under pressure using C8 complex and Me2AlCl as co-catalysts:

[0282] 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 one backfilling with ethylene. Under an ethylene atmosphere, 25 mL of toluene, 25 mL of a 1 μmol toluene solution of catalyst C8, 1.0 mL of a 1.00 mol / L toluene solution of co-catalyst Me2AlCl, and 50 mL of toluene were sequentially added to the 250 mL stainless steel autoclave, at which point the Al / Ni ratio was 500:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30 °C, ethylene was introduced into the reactor, and the polymerization reaction began. An ethylene pressure of 10 atm was maintained at 30 °C, and stirring was continued for 30 min. After the reaction was completed, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0283] Polymerization activity: 7.5 × 10 6 g·mol -1 (Ni)·h -1 Polymer T m =62.7,114.4℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =13.5×10 5 g·mol -1 PDI1 = 2.3; M w2 =0.024×10 5 g·mol -1 PDI2 = 1.9 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0284] Take 40 mg of the obtained polymer, dissolve it in 5 mL of deuterated tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2000 times yielded peak shifts between 10-40 ppm, indicating shifts in methyl, methylene, and methine groups. This confirms the obtained polymer is branched polyethylene with a moderate degree of branching (128B / 1000C) and a long-chain proportion of 4.4% (see details). Figure 4 ).

[0285] The obtained polyethylene was subjected to mechanical tensile property tests. Five tests were conducted, and the average value was taken. The tensile strength was 6.82 MPa, and the elongation at break was 539% (see the mechanical property test spectrum for details). Figure 7 The obtained polymer was subjected to stress-strain recovery tests, and the elastic recovery rate was 75% (see mechanical property test spectrum for details). Figure 8 ).

[0286] Example 22

[0287] Ethylene polymerization under pressure using C8 complex and Me2AlCl as co-catalysts:

[0288] a) Basically the same as Example 21, except that the polymerization temperature is 20°C. Polymerization activity: 6.6 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =92.4,115.0℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =22.1×10 5 g·mol -1 PDI1 = 2.0; M w2 =0.024×10 5 g·mol -1 PDI2 = 2.3 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0289] b) Basically the same as Example 21, except that the polymerization temperature is 40°C. Polymerization activity: 7.4 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =42.5℃, polymer molecular weight M w1 =11.9×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.013×10 5 g·mol -1 PDI2 = 1.6.

[0290] c) Basically the same as Example 21, except that the polymerization temperature is 50°C. Polymerization activity: 5.4 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =44.6℃, polymer molecular weight M w1 =10.4×10 5 g·mol -1 PDI1 = 2.9; M w2 =0.0075×10 5 g·mol -1 PDI2 = 1.5.

[0291] d) Basically the same as Example 21, except that the polymerization temperature is 60℃. Polymerization activity: 4.1 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =26.1℃, polymer molecular weight M w1 =10.0×10 5 g·mol -1 PDI1 = 2.5; M w2 =0.0058×10 5 g·mol -1 PDI2 = 1.4.

[0292] The obtained polyethylene was subjected to mechanical tensile property tests. Five tests were conducted, and the average value was taken. The tensile strength was 2.79 MPa, and the elongation at break was 633% (see the mechanical property test spectrum for details). Figure 7 The obtained polymer was subjected to stress-strain recovery tests, and the elastic recovery rate was 83% (see mechanical property test spectrum for details). Figure 9 ).

[0293] e) Basically the same as Example 21, except that the polymerization temperature is 80°C. Polymerization activity: 2.9 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =16.2℃, polymer molecular weight M w =7.2×10 5 g·mol -1 PDI = 2.3. The obtained polymer underwent stress-strain recovery testing, and the elastic recovery rate was 87% (see mechanical property test spectrum for details). Figure 10 ).

[0294] f) Basically the same as Example 21, except that: the amount of co-catalyst used is 0.5 mL of Me2AlCl (1.00 mol / L, toluene solution), making Al / Ni = 250:1. Polymerization activity: 3.9 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =70.3, 114.0℃, polymer molecular weight M w1 =14.0×10 5 g·mol -1 PDI1 = 2.0; M w2 =0.014×10 5 g·mol -1 PDI2 = 1.5.

[0295] g) Basically the same as Example 21, except that: the amount of co-catalyst used is 1.5 mL of Me2AlCl (1.00 mol / L, toluene solution), making Al / Ni = 750:1. Polymerization activity: 7.0 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =58.6℃, polymer molecular weight M w1 =9.5×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.011×10 5 g·mol -1 PDI2 = 1.6.

[0296] h) Basically the same as Example 21, except that: the amount of co-catalyst used is 2.0 mL of Me2AlCl (1.00 mol / L, toluene solution), making Al / Ni = 1000:1. Polymerization activity: 6.4 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =83.9, 119.3℃, polymer molecular weight M w1 =8.2×10 5 g·mol -1 PDI1 = 2.0; M w2 =0.016×10 5 g·mol -1 PDI2 = 1.7.

[0297] i) Basically the same as Example 21, except that: the amount of co-catalyst used is 2.5 mL of Me2AlCl (1.00 mol / L, toluene solution), making Al / Ni = 1250:1. Polymerization activity: 4.9 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =74.4, 113.5℃, polymer molecular weight M w1 =5.8×10 5 g·mol -1 PDI1 = 1.9; M w2 =0.013×10 5 g·mol -1 PDI2 = 1.5.

[0298] j) Basically the same as Example 21, except that the ethylene pressure is 5 atm. Polymerization activity: 4.7 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =62.5, 115.9℃, M w =7.8×10 5 g·mol -1 PDI = 3.5.

[0299] Example 23

[0300] Ethylene polymerization under pressure using complex C1 and Me2AlCl as co-catalysts:

[0301] Basically the same as Example 21, except that the main catalyst is C1. Polymerization activity: 7.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =50.9℃, polymer molecular weight M w1 =9.9×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.014×10 5 g·mol -1 PDI2 = 1.5. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 5.05 MPa, and the elongation at break was 474% (see the mechanical property test spectrum for details). Figure 7 ).

[0302] Example 24

[0303] Ethylene polymerization under pressure using complex C2 and Me2AlCl as co-catalysts:

[0304] Basically the same as Example 21, except that the main catalyst is C2. Polymerization activity: 6.7 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =50.3, 84.4℃, polymer molecular weight M w1 =9.1×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.012×10 5 g·mol -1PDI2 = 1.4. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 6.83 MPa, and the elongation at break was 616% (see the mechanical property test spectrum for details). Figure 7 ).

[0305] Example 25

[0306] Ethylene polymerization under pressure using complex C3 and Me2AlCl as co-catalysts:

[0307] Basically the same as Example 21, except that the main catalyst is C3. Polymerization activity: 8.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =48.3℃, polymer molecular weight M w1 =11.1×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.051×10 5 g·mol -1 PDI2 = 1.4.

[0308] Take 40 mg of the obtained polymer, dissolve it in 5 mL of deuterated tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2000 times yielded peak shifts between 10-40 ppm, indicating shifts in methyl, methylene, and methine groups. This confirms the obtained polymer is branched polyethylene with a high degree of branching (129B / 1000C) and a long-chain proportion of 5.56% (see details). Figure 3 ).

[0309] Example 26

[0310] Ethylene polymerization under pressure using C4 complex and Me2AlCl as co-catalysts:

[0311] Basically the same as Example 21, except that the main catalyst is C4. Polymerization activity: 8.3 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =51.0℃, polymer molecular weight M w1 =9.3×10 5 g·mol -1 PDI1 = 3.0; M w2 =0.019×10 5 g·mol -1 PDI2 = 1.8.

[0312] Example 27

[0313] Ethylene polymerization under pressure using complex C5 and Me2AlCl as co-catalysts:

[0314] The process is basically the same as in Example 21, except that the main catalyst is C5. Polymerization activity: 7.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =51.0℃, polymer molecular weight M w1 =13.2×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.012×10 5 g·mol -1 PDI2 = 1.3.

[0315] Example 28

[0316] Ethylene polymerization under pressure using C6 complex and Me2AlCl as co-catalysts:

[0317] Basically the same as Example 21, except that the main catalyst is C6. Polymerization activity: 7.2 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =48.8℃, polymer molecular weight M w1 =7.4×10 5 g·mol -1 PDI1 = 2.0; M w2 =0.010×10 5 g·mol -1 PDI2 = 1.4. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 4.60 MPa, and the elongation at break was 418% (see the mechanical property test spectrum for details). Figure 7 ).

[0318] Example 29

[0319] Ethylene polymerization under pressure using C7 complex and Me2AlCl as co-catalysts:

[0320] Basically the same as Example 21, except that the main catalyst is C7. Polymerization activity: 7.6 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m=47.3℃, polymer molecular weight M w1 =10.6×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.010×10 5 g·mol -1 PDI2 = 1.4. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 5.39 MPa, and the elongation at break was 533% (see the mechanical property test spectrum for details). Figure 7 ).

[0321] Example 30

[0322] Ethylene polymerization under pressure using complex C1 and AlMe3 as co-catalysts:

[0323] 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 one backfilling with ethylene. Under an ethylene atmosphere, 25 mL of toluene, 25 mL of a toluene solution of catalyst C1 (0.5 μmol), 0.25 mL of co-catalyst AlMe3 (2.00 mol / L, n-hexane solution), and 50 mL of toluene were sequentially added to the 250 mL stainless steel autoclave, at which point the Al / Ni ratio was 500:1. Mechanical stirring was initiated and maintained at 400 rpm. When the polymerization temperature reached 30 °C, ethylene was introduced into the reactor, and the polymerization reaction began. An ethylene pressure of 10 atm was maintained at 30 °C, and stirring was continued for 30 min. After the reaction was completed, the ethylene supply was stopped, the reactor was cooled, and the atmosphere was vented. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, vacuum dried to constant weight, and weighed.

[0324] Polymerization activity: 3.9 × 10 6 g·mol -1 (Ni)·h -1 Polymer T m =77.9℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w1 =17.4×10 5 g·mol -1 PDI1 = 2.4; M w2 =0.026×10 5 g·mol -1 PDI2 = 1.8 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0325] Example 31

[0326] Ethylene polymerization under pressure using complex C2 and AlMe3 as co-catalysts:

[0327] Basically the same as Example 30, except that the main catalyst is C2. Polymerization activity: 5.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =78.1, 125.2℃, polymer molecular weight M w1 =20.3×10 5 g·mol -1 PDI1 = 2.3; M w2 =0.027×10 5 g·mol -1 PDI2 = 1.9.

[0328] Example 32

[0329] Ethylene polymerization under pressure using C3 complex and AlMe3 co-catalyst:

[0330] The process is basically the same as in Example 30, except that the main catalyst is C3. Polymerization activity: 4.7 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =76.9, 128.6℃, polymer molecular weight M w1 =13.5×10 5 g·mol -1 PDI1 = 2.3; M w2 =0.021×10 5 g·mol -1 PDI2 = 1.6.

[0331] Take 40 mg of the obtained polymer, dissolve it in 5 mL of deuterated tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2000 times yielded peak shifts between 10-40 ppm, indicating shifts in methyl, methylene, and methine groups. This confirms the obtained polymer is branched polyethylene with a high degree of branching (10⁷ B / 1000 C) and a long-chain proportion of 15.2% (see details). Figure 5 ).

[0332] Example 33

[0333] Ethylene polymerization under pressure using C4 complex and AlMe3 co-catalyst:

[0334] The process is basically the same as in Example 30, except that the main catalyst is C4. Polymerization activity: 1.7 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =96.1, 119.0℃, polymer molecular weight M w1 =17.7×10 5 g·mol -1 PDI1 = 2.2; M w2 =0.040×10 5 g·mol -1 PDI2 = 2.1.

[0335] Example 34

[0336] Ethylene polymerization under pressure using C5 complex and AlMe3 co-catalyst:

[0337] The process is basically the same as in Example 30, except that the main catalyst is C5. Polymerization activity: 1.9 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =87.8, 121.8℃, polymer molecular weight M w1 =17.9×10 5 g·mol -1 PDI1 = 2.4; M w2 =0.055×10 5 g·mol -1 PDI2 = 2.0.

[0338] Example 35

[0339] Ethylene polymerization under pressure using C6 complex and AlMe3 co-catalyst:

[0340] The process is basically the same as in Example 30, except that the main catalyst is C6. Polymerization activity: 1.9 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =88.5, 118.0℃, polymer molecular weight M w1 =19.8×10 5 g·mol -1 PDI1 = 2.1; M w2 =0.062×10 5 g·mol -1 PDI2 = 1.8.

[0341] Example 36

[0342] Ethylene polymerization under pressure using C7 complex and AlMe3 co-catalyst:

[0343] Basically the same as Example 30, except that the main catalyst is C7. Polymerization activity: 3.4 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =84.8, 116.6℃, polymer molecular weight M w1 =26.2×10 5 g·mol -1 PDI1 = 1.7; M w2 =0.050×10 5 g·mol -1 PDI2 = 1.9.

[0344] Example 37

[0345] Ethylene polymerization under pressure using C8 complex and AlMe3 co-catalyst:

[0346] The process is basically the same as in Example 30, except that the main catalyst is C8. Polymerization activity: 3.0 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =85.4, 120.6℃, polymer molecular weight M w1 =35.8×10 5 g·mol -1 PDI1 = 1.6; M w2 =0.067×10 5 g·mol -1 PDI2 = 2.1.

[0347] Take 40 mg of the obtained polymer, dissolve it in 5 mL of deuterated tetrachloroethane, and test the polymer at 100 °C. 13 C data. Signal accumulation of 2000 times yielded peak shifts between 10-40 ppm, indicating shifts in methyl, methylene, and methine groups. This confirms the obtained polymer is branched polyethylene with a high degree of branching (56B / 1000C) and a long-chain proportion of 6.7% (see details). Figure 6 ).

[0348] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0349] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. An asymmetric binuclear nickel complex containing anisoligands, having the structure shown in formula (I): Formula (I) wherein, R 1 the same or different, each independently selected from hydrogen, Ci-C6alkyl, Ci-C6alkoxy or C3-C10cycloalkyl; R 2 The group is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxyl, mercapto, nitro or C3-C10 cycloalkyl, wherein the C1-C6 alkyl, C1-C6 alkoxy, hydroxyl or mercapto is optionally substituted by one or more substituents selected from C1-C6 alkyl, C3-C10 cycloalkyl or R', where R' is selected from C3-C10 halocycloalkyl; R 3 They may be the same or different, and each is independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C10 cycloalkyl; R 4 selected from C1-C6alkyl or C3-C10cycloalkyl; X is the same or different, and is selected from halogens.

2. The binuclear nickel complex according to claim 1, wherein, said R 1 the same or different, are selected from hydrogen or Ci-C6alkyl; said R 2 selected from hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, halogen, hydroxyl, thiol, nitro, C3-C10-cycloalkyl or -O-C3-C10-cycloalkyl; said R 3 the same or different, are selected from C1-C6alkyl; said R 4 selected from C1-C6alkyl; The X may be the same or different, and is selected from fluorine, chlorine or bromine.

3. The dinuclear nickel complex of claim 2, wherein, The R 2 It is selected from hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, hydroxy, mercapto, nitro, trifluoromethoxy, fluorine, chlorine, bromine, iodine, cyclopropyl, or cyclohexyl.

4. The binuclear nickel complex according to claim 1, wherein, said R 1 the same or different, are selected from hydrogen or Ci-C6alkyl; The R 2 Selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, hydroxyl, mercapto or nitro; said R 3 the same or different, are selected from C1-C6alkyl; said R 4 selected from C1-C6alkyl; X is selected from chlorine or bromine.

5. The dinuclear nickel complex of claim 4, wherein, The C1-C6 haloalkoxy groups are selected from C1-C6 fluoroalkoxy groups.

6. The binuclear nickel complex according to claim 4, wherein, said R 1 identical or different, are selected from hydrogen or C1-C4alkyl; said R 2 selected from hydrogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4fluoroalkoxy, fluorine, chlorine, bromine or nitro; said R 3 the same or different, are selected from C2-C4alkyl; The R 4 Selected from C1 to C4 alkyl groups; X is selected from chlorine or bromine.

7. The dinuclear nickel complex according to any one of claims 1 to 6, wherein, The binuclear nickel complex is selected from one of the following:

8. A process for the preparation of the heteroligand-containing unsymmetrical dinuclear nickel complex of any one of claims 1 to 7, wherein, The preparation method includes the following steps: S1: The acenaphthene monoketone of the structure shown in formula (III) undergoes a ketamine condensation reaction with the benzidine of the structure shown in formula (IV) to obtain the acenaphthene diimine of the structure shown in formula (V); S2: The acenaphthene diimide undergoes a ketamine condensation reaction with an acylpyridine of formula (VI) to obtain a ligand compound of formula (II); and S3: The ligand compound undergoes a complexation reaction with a nickel-containing reagent to obtain the binuclear nickel complex; Among them, R 1 R 2 R 3 and R 4 As defined in any one of claims 1-7.

9. The production method according to claim 8, wherein The nickel-containing reagent is selected from nickel-containing halides.

10. The production method according to claim 9, wherein, The nickel-containing reagent is selected from (DME)NiBr2, NiCl2·6H2O or NiBr2.

11. The preparation method according to any one of claims 8-10, wherein, In step S1, the acenaphthene monoketone and benzidine undergo a ketamine condensation reaction in a first organic solvent in the presence of a first catalyst. In step S2, the acenaphthene diimide and acylpyridine undergo a ketamine condensation reaction in a second organic solvent in the presence of a second catalyst; and In step S3, the ligand compound and the nickel-containing reagent undergo a complexation reaction in a third organic solvent.

12. The method of making according to claim 11, wherein, The first organic solvent and the second organic solvent are selected from aromatic organic solvents.

13. The method of making according to claim 12, wherein, The first organic solvent and the second organic solvent are selected from toluene.

14. The method of making according to claim 11, wherein, The first catalyst and the second catalyst are selected from p-toluenesulfonic acid.

15. The method of making according to claim 11, wherein, The molar ratio of acenaphthene monoketone to benzidine is 1:1-2.

16. The method of making according to claim 11, wherein, The ketamine condensation reaction in step S1 is carried out under reflux for 6–24 h.

17. The method of making of claim 11, wherein, The molar ratio of acenaphthene to acylpyridine is 1:1 to 10.

18. The method of making of claim 11, wherein, The ketone-amine condensation reaction in step S2 is carried out under reflux for 6–24 h.

19. The method of making according to claim 11, wherein, The third organic solvent is selected from one or more of haloalkanes and alcohols.

20. The method of making according to claim 19, wherein, The third organic solvent is selected from one or more of dichloromethane and ethanol.

21. The method of making of claim 11, wherein, The molar ratio of the ligand compound to the nickel-containing reagent is 1:2-3.

22. The method of making according to claim 11, wherein, The complexation reaction is carried out at a temperature of 0–35°C for 8–16 h.

23. An asymmetric binuclear ligand compound containing an heteroligand, having the structure shown in formula (II): Equation (II) wherein, R 1 , R 2 , R 3 and R 4 are as defined in any of claims 1 to 7.

24. The binuclear ligand compound according to claim 23, wherein, The binuclear ligand compound is selected from one of the following:

25. A catalyst composition comprising a procatalyst and optionally a cocatalyst, wherein, The main catalyst is the asymmetric binuclear nickel complex containing heteroligands as described in any one of claims 1-7.

26. The catalyst composition of claim 25, wherein, The cocatalyst is selected from one or more of aluminoxane cocatalysts, alkylaluminum cocatalysts, and alkylaluminum chloride cocatalysts.

27. The catalyst composition of claim 26, wherein, The aluminum oxane cocatalyst is selected from one or more of methylaluminoxane and triisobutylaluminum-modified methylaluminoxane; the alkylaluminum cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, and triisobutylaluminum; the chlorinated alkylaluminum cocatalyst is selected from one or more of diethylaluminum chloride, dimethylaluminum chloride, triethylaluminum trichloride, and diethylaluminum dichlorochloride.

28. The catalyst composition of claim 27, wherein, When the cocatalyst is selected from methylaluminoxane, the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 1000–3000:

1. When the cocatalyst is selected from triisobutylaluminum-modified methylaluminoxane, the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 1000-3000:

1. When the cocatalyst is selected from dimethylaluminum chloride, the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 100-2000:

1. When the cocatalyst is selected from trimethylaluminum, the molar ratio of metallic Al to the central metallic Ni of the binuclear nickel complex is 100–2000:

1.

29. Use of the asymmetric binuclear nickel complex containing heteroligands according to any one of claims 1-7, or the catalyst composition according to any one of claims 25-28, in the catalytic polymerization of olefins.

30. The use of claim 29, wherein, The application is for use in the catalytic polymerization of ethylene.

31. The use of claim 30, wherein, The ethylene polymerization is either homopolymerization of ethylene or copolymerization of ethylene with α-olefins.

32. The use of claim 31, wherein, The α-olefin is a C3 to C20 α-olefin.

33. An olefin polymerization method, using the asymmetric binuclear nickel complex containing heteroligands as described in any one of claims 1-7, or the catalyst composition as described in any one of claims 25-28 as a catalyst.

34. The olefin polymerization process of claim 33, wherein, The olefin polymerization is ethylene polymerization.

35. The olefin polymerization process of claim 34, wherein, The ethylene polymerization is either homopolymerization of ethylene or copolymerization of ethylene with α-olefins.

36. The olefin polymerization process of claim 35, wherein, The α-olefin is a C3 to C20 α-olefin.

37. A method for preparing polyethylene, wherein the asymmetric binuclear nickel complex containing heteroligands as described in any one of claims 1-7, or the catalyst composition as described in any one of claims 25-28, is used as a catalyst to polymerize ethylene under its catalytic action to prepare polyethylene.

38. The method of manufacturing according to claim 37, wherein, The polymerization reaction is carried out at a temperature of 20–80°C.

39. The method of manufacturing according to claim 37, wherein, The polymerization reaction takes 5 to 100 minutes.

40. The method of manufacturing according to claim 37, wherein, The polymerization reaction is carried out at a pressure of 0.3–20 atm.

41. The preparation method according to claim 37, wherein, The polymerization reaction is carried out in a fourth organic solvent, which is selected from one or more of toluene, xylene, dichloromethane, tetrahydrofuran, n-hexane, or cyclohexane.

42. The preparation method according to claim 37, wherein, The polyethylene is bimodal polyethylene.

Images