An amine group-containing unsymmetrical acenyl alpha-diimine nickel complex, a preparation method and use thereof

Abstract

The application provides an amine-containing unsymmetrical acenyl alpha-diimine nickel complex having a structure shown in formula (I). The application also provides a preparation method and use of the nickel complex. The application further provides a catalyst composition and an olefin polymerization method, in particular, a polyethylene preparation method. The nickel complex provided by the application has a novel structure, has high catalytic activity and good thermal stability when used for catalyzing olefin polymerization (in particular, ethylene polymerization), and has the potential for further preparing a heterogeneous covalent supported catalyst. In addition, the preparation method of the nickel complex provided by the application is simple, the reaction condition is mild, the operation is simple and easy to control, and the method has strong industrial practicability.

Description

Technical Field

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

[0002] Advances in polyolefin industrial technology have largely benefited from the development of polyolefin catalysts. IHS Markit data shows that in 2020, polyolefins produced through catalytic processes accounted for 87% of total polyolefin production, indicating that the design and synthesis of novel polyolefin catalysts is a crucial step in further advancing polyolefin industrial technology. Currently, industrialized polyethylene catalysts mainly include Phillips catalysts, Ziegler-Natta catalysts, and metallocene catalysts. The design and development of these catalysts have greatly promoted the production and application of commercial high-performance polyolefin products.

[0003] In recent years, post-transition metal catalysts have attracted widespread attention and are developing rapidly due to their explorable mechanisms, unique tolerance to polar monomers, and unusual catalytic performance. As researchers delve deeper into the relationship between the structure and catalytic performance of post-transition metal catalysts, an increasing number of excellent ligand frameworks have been proposed and extensively studied, mainly including α-diimine, pyridylimine, phenoxyimine, and pyridyldiimine ligands. Among them, Brookhart-type α-diimine nickel complexes (A, Formula 1) possess the ability to convert a single ethylene monomer into polyethylene with varying degrees of branching (1.2–300 branches / 1000 carbons) due to their unique chain-walking mechanism (J. Am. Chem. Soc., 1995, 117, 6414).

[0004] The inventors' research group has been dedicated to the design and development of olefin polymerization catalysts and the exploration of catalytic processes, conducting extensive research and structural optimization work on post-transition nickel complexes. For Brookhart-type α-diimine nickel complexes, modification of the ligand structure mainly involves systematic modification of the ligand skeleton and the type of N-aryl substituents, thereby regulating the catalytic performance (polymerization activity and polymer properties) of the complex. The mode of the ligand skeleton structure determines the coordination environment of the metal center, while the regulation of the N-aryl substitution mode in terms of steric and electronic effects can directly determine the properties of the metal center, thus regulating the catalytic activity, thermal stability, molecular weight, and various microstructural properties of the resulting polyethylene.

[0005] For example, when the inventors' research group placed bulky diphenylmethyl groups and R groups with different electronic properties at the ortho and para positions of the N-aryl group, respectively, they could adjust the catalytic activity and polymer structure by changing the electronic properties of the para-substituents in the acenaphthene α-diimine nickel complex (B, Formula 1) while ensuring the thermal stability of the complex (Coord. Chem. Rev., 2017, 350, 68–83). In general, all nickel complexes exhibit excellent catalytic activity in ethylene polymerization. Nickel complexes containing electron-donating groups show better catalytic activity and thermal stability than those with electron-withdrawing groups, while the electron-withdrawing groups have a direct impact on polymer properties, especially molecular weight and degree of branching.

[0006]

[0007] All the complexes B (Formula 1) mentioned above have achieved structural optimization of one-sided N-aryl groups, but lack discussion on the steric hindrance effect of the para-substituents of the N-aryl group. Furthermore, as a representative type of homogeneous post-transition metal catalysts, structural modification can only partially ensure sufficient thermal stability while maintaining catalytic activity. Recently, the inventors' research group synthesized a class of amine-terminated pyridineimine nickel complexes and demonstrated that the presence of the amine group is beneficial for improving the catalytic activity of the complex and the molecular weight of the resulting polymer (ACS Omega, 2021, 6, 30157-30172). Moreover, the presence of the amine group makes high-concentration covalent loading of homogeneous nickel complex catalysts on certain supports possible.

[0008]

[0009] Although researchers have recognized the need to introduce sterically hindered N,N-diaryl groups into the catalyst structure to achieve high thermal stability and activity of the catalyst, as well as the high molecular weight (M) of the resulting polymer, w ) and high melting temperature (T m However, existing novel α-diimine complexes still suffer from the problem of excessively low molecular weight polyethylene and low catalytic activity at higher operating temperatures. In fact, the steric hindrance effect of N-aryl para-substituents also needs to be considered when designing catalyst structures, as the steric hindrance of para-substituents can indirectly push N-aryl ortho-substituents in space, thus affecting the protection of the active center in the axial position of the coordination plane. Furthermore, for such catalysts to achieve industrialization, they should possess the ability to produce branched polyethylene with controllable microstructure (including branching degree, molecular weight, and molecular weight distribution) and controllable mechanical properties while maintaining high catalytic activity and thermal stability.

[0010] Besides the aforementioned method of modifying the structure of olefin polymerization catalysts to improve the catalytic performance of complexes, homogeneous catalyst loading is also a feasible approach. Covalent loading is more stable and efficient than conventional force-based loading, and allows for a larger loading capacity of the target catalyst. Summary of the Invention

[0011] To overcome the shortcomings of existing technologies, the inventors, based on the important role of the presence of "amine group" and "N-aryl para-sterically hindered group" in the structural modification of catalysts for olefin polymerization, and combined with the tunable electronic properties of the para-substituent on the other side of the N-aryl group, combined the "amine group" strategy and the "N-aryl para-sterically hindered group" strategy by modifying the para-substituents on both sides of the N-aryl group, thus arriving at the present invention.

[0012] Therefore, one object of the present invention is to provide an amine-containing asymmetric acenaphthene α-diimine nickel complex that exhibits high activity and high thermal stability when used as an olefin polymerization catalyst (especially an ethylene polymerization catalyst), and that the nickel complex also has the potential to be further prepared into heterogeneous covalently supported catalysts.

[0013] Another object of the present invention is to provide a method for preparing the nickel complex and its uses.

[0014] The first aspect of the present invention provides an amino-containing asymmetric acenaphthene α-diimine nickel complex having the structure shown in formula (I):

[0015]

[0016] Among them, R 1 Same or different, R 3 Same or different, R 1 R 2 and R 3 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;

[0017] X is the same or different, and is selected from halogens.

[0018] In some preferred embodiments, the R 1 Same or different, selected from hydrogen or C1-C6 alkyl;

[0019] The R 2The alkyl group is 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, it is selected from hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, hydroxyl, mercapto, nitro, trifluoromethoxy, fluorine, chlorine, bromine, iodine, cyclopropyl, cyclohexyl, phenyl, benzyl, diphenylmethyl or di(4-fluorophenyl)methyl;

[0020] The R 3 Same or different, selected from hydrogen or C1-C6 alkyl;

[0021] The X may be the same or different, and is selected from fluorine, chlorine or bromine.

[0022] 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;

[0023] The R 2 It is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy (e.g., 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;

[0024] The R 3 Same or different, selected from C1 to C6 alkyl groups, for example, selected from C2 to C4 alkyl groups;

[0025] X is selected from chlorine or bromine, for example, from bromine.

[0026] In some preferred embodiments, the complex is selected from:

[0027]

[0028]

[0029] Specifically, the complexes shown in the table above have the following group definitions:

[0030] C1:R 1 =H;R 2 =Me;R 3 = i Pr; X is Br;

[0031] C2:R 1 =H;R 2 =i Pr;R 3 = i Pr; X is Br;

[0032] C3:R 1 =H;R 2 = t Bu;R 3 = i Pr; X is Br;

[0033] C4:R 1 =H;R 2 =OMe;R 3 = i Pr; X is Br;

[0034] C5:R 1 =H;R 2 =OCF3;R 3 = i Pr; X is Br;

[0035] C6:R 1 =H;R 2 =Cl;R 3 = i Pr; X is Br;

[0036] C7:R 1 =H;R 2 =F;R 3 = i Pr; X is Br;

[0037] C8:R 1 =H;R 2 =NO2; R 3 = i Pr; X is Br.

[0038] A second aspect of the present invention provides a method for preparing the amine-containing asymmetric acenaphthene α-diimine nickel complex according to any one of the above-described technical solutions, wherein the preparation method includes the following steps:

[0039] S1: The acenaphthene monoketone of formula (III) undergoes a ketamine condensation reaction with benzidine of formula (IV) to obtain a ligand compound of formula (II); and

[0040] S2: The ligand compound undergoes a complexation reaction with a nickel-containing reagent to obtain the nickel complex;

[0041]

[0042]

[0043] Among them, R 1 R 2 and R 3 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 acenaphthenic ketone and benzidine undergo a ketamine condensation reaction in a first organic solvent in the presence of a catalyst.

[0046] In some preferred embodiments, the first organic solvent is selected from aromatic organic solvents commonly used in the art, such as toluene.

[0047] In some preferred embodiments, the catalyst is selected from ketamine condensation catalysts commonly used in the art, such as p-toluenesulfonic acid.

[0048] 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.

[0049] In some preferred embodiments, the ketamine condensation reaction is carried out under reflux for 6 to 24 hours, for example, under reflux for 6 to 12 hours.

[0050] In some preferred embodiments, in step S2, the ligand compound undergoes a complexation reaction with a nickel-containing reagent in a second organic solvent.

[0051] In some preferred embodiments, the second 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.

[0052] In some more preferred embodiments, the molar ratio of the ligand compound to the nickel-containing reagent is 1 to 2:1, for example, 1 to 1.5:1.

[0053] 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).

[0054] 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.

[0055] In some preferred embodiments, the ketamine condensation reaction is completed by the following purification process: the first organic solvent is removed from the reaction system to obtain a crude product, which is then subjected to column chromatography (e.g., basic alumina column) using a mixed solvent of petroleum ether and ethyl acetate (e.g., a volume ratio of 25:1) as the eluent. The desired fraction is collected, and the eluent is removed to obtain the purified ligand compound.

[0056] 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 nickel complex.

[0057] In the preparation method provided by the present invention, both the acenaphthenic acid monoketone with the structure shown in formula (III) and the benzidine with the structure shown in formula (IV) can be obtained commercially or can be prepared by referring to the literature, such as the preparation process of acenaphthenic acid monoketone disclosed in Chinese Patent CN 108794545B.

[0058] 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.

[0059]

[0060] 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.

[0061] A third aspect of the present invention provides an amino-containing asymmetric acenaphthenic α-diimine ligand compound having the structure shown in formula (II):

[0062]

[0063] Among them, R 1 R 2 and R 3 Each is independently defined as described in any of the above technical solutions.

[0064] In some preferred embodiments, the ligand compound is selected from:

[0065]

[0066]

[0067] Specifically, the ligand compounds shown in the table above have the following group definitions:

[0068] L1:R 1 =H;R 2 =Me;R 3 = i Pr;

[0069] L2:R 1 =H;R 2 = i Pr;R 3 = i Pr;

[0070] L3:R 1 =H;R 2 = t Bu;R 3 = i Pr;

[0071] L4:R 1 =H;R 2 =OMe;R 3 = i Pr;

[0072] L5:R 1 =H;R 2 =OCF3;R 3 = i Pr;

[0073] L6:R 1 =H;R 2 =Cl;R 3 = i Pr;

[0074] L7:R 1 =H;R 2 =F;R 3 = i Pr;

[0075] L8:R 1 =H;R 2 =NO2; R 3 = i Pr.

[0076] 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 amine-containing asymmetric acenaphthene α-diimine nickel complex as described in any of the above-described technical solutions.

[0077] 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.

[0078] 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).

[0079] 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 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.

[0080] 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 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.

[0081] 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 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.

[0082] 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 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.

[0083] The fifth aspect of the present invention provides the use of the amine-containing asymmetric acenaphthene α-diimine nickel complex 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.

[0084] In some preferred embodiments, the ethylene polymerization is a homopolymerization of ethylene or a copolymerization of ethylene with an α-olefin.

[0085] In some more preferred embodiments, the α-olefin is a C3 to C20 α-olefin, such as a C3 to C12 α-olefin.

[0086] The sixth aspect of the present invention provides an olefin polymerization method, wherein the polymerization method uses an amine-containing asymmetric acenaphthene α-diimine nickel complex as described in any one of the above technical solutions, or a catalyst composition as described in any one of the above technical solutions, as a catalyst.

[0087] In some preferred embodiments, the olefin polymerization is ethylene polymerization.

[0088] In some preferred embodiments, the ethylene polymerization is a homopolymerization of ethylene or a copolymerization of ethylene with an α-olefin.

[0089] In some further preferred embodiments, the α-olefin is a C3 to C20 α-olefin, such as a C3 to C12 α-olefin.

[0090] A seventh aspect of the present invention provides a method for preparing polyethylene, wherein the method uses an amine-containing asymmetric acenaphthene α-diimine nickel complex as described in any one of the above technical solutions, or a catalyst composition as described in any one of the above technical solutions, as a catalyst, and ethylene is polymerized under its catalytic action to prepare polyethylene.

[0091] In some preferred embodiments, the polymerization reaction is carried out at a temperature of 20–80°C, for example, 20–60°C.

[0092] In some preferred embodiments, the polymerization reaction takes 5 to 100 minutes, for example, 20 to 50 minutes.

[0093] 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.

[0094] In some preferred embodiments, the polymerization reaction is carried out in a third organic solvent selected from one or more of toluene, xylene, dichloromethane, tetrahydrofuran, n-hexane, or cyclohexane.

[0095] In some preferred embodiments, the polymerization reaction is carried out in an ethylene atmosphere.

[0096] The technical solution provided by this invention has the following advantages:

[0097] (1) The nickel complex structure provided by the present invention contains both an "amine group" and an "N-aryl para-sterically hindered group", and the other side of the N-aryl group has a para-substituent (i.e., R). 2 This allows for tunable electrical properties. The nickel complex has a novel structure, a simple preparation method, mild reaction conditions, a short production cycle, simple and easy operation and control, and low cost, thus possessing strong industrial applicability.

[0098] (2) The 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 the nickel complex in catalyzing ethylene polymerization can reach 17.1 × 10⁻⁶. 6 g PE mol -1 (Ni)h -1 Therefore, it has become one of the nickel catalysts with the highest catalytic activity currently available.

[0099] (3) The presence of N-biphenyl groups (i.e., the presence of N-aryl para-substituents) in the nickel complex provided by this invention enables the complex to possess good thermal stability. For example, when AlMe3 is used as a co-catalyst, the activity of the nickel complex in catalyzing ethylene polymerization can still reach as high as 5.2 × 10⁻⁶ at relatively high temperatures (60 °C). 6 g PE mol -1 (Ni)h -1 When the polymerization conditions are changed, the weight-average molecular weight of polyethylene prepared by this catalyst system ranges from 2.2 to 26.9 × 10⁻⁶. 5 g mol -1 The molecular weight of the resulting polyethylene elastomer fluctuates between 1.9 and 2.7, with most cases having a molecular weight of over one million. This demonstrates a strong ability to regulate the molecular weight of polyethylene, indicating that the polymer product is a potential high-value-added ultra-high molecular weight polyethylene with great potential for industrial applications.

[0100] (4) The polyethylene prepared by the nickel complex or catalyst composition provided by this invention has a melting temperature between 41.9 and 100.5 °C, indicating that the obtained polyethylene elastomer material has a wide range of applications. Furthermore, this type of polyethylene elastomer material also has high molecular weight and high branching degree, thus exhibiting good mechanical properties. Tensile fracture test and elastic recovery test experiments show that the tensile strength of this material can reach 4.81 MPa, the elongation at break can reach 410%, and the elastic recovery rate is as high as 80%.

[0101] (5) The nickel complex provided by this invention has a single catalytic active center, and the molecular weight of the polymer (2.2–26.9 × 10⁻⁶) can be adjusted by changing the electronic properties of the N-aryl para-substituents and the polymerization conditions. 5 g·mol -1 Effective regulation of branching degree (68–153B / 1000C).

[0102] (6) The presence of the active group NH2 on the nickel complex structure provided by the present invention has a positive effect on improving the polymerization activity, and helps to achieve covalent loading of homogeneous catalyst molecules on inorganic components such as silica and alumina, opening up new ways for further improvement of nickel catalyst performance (such as catalytic activity, thermal stability, etc.), and also expanding the types and application range of nickel catalysts. Attached Figure Description

[0103] Figure 1 This is a schematic diagram of the molecular structure obtained from the C8 single crystal in Example 16.

[0104] Figure 2 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 20.

[0105] Figure 3 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 25.

[0106] Figure 4 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 32.

[0107] Figure 5 The image shows the heated carbon NMR spectrum of the polyethylene obtained in Example 37.

[0108] Figure 6 The tensile properties of polyethylene obtained in Examples 30, 31, and 35-37 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).

[0109] Figure 7 The figure shows the stress-strain recovery test results of the polyethylene obtained in Example 37. Detailed Implementation

[0110] the term

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] The term “halogen” as used alone or in combination in this article refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0119] The technical solution of the present invention will be further described in detail below with reference to specific embodiments.

[0120] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0121] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0122] Unless otherwise specified, all concentrations in the following examples are molar concentrations.

[0123] 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.

[0124] The structures of all the synthesized complexes described below were confirmed by infrared and elemental analysis.

[0125] The synthetic routes for the amine-containing asymmetric acenaphthene α-diimine nickel complexes in the following examples are as follows:

[0126]

[0127] Example 1

[0128] The 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[L1] as shown in formula (II), wherein R 1 For hydrogen, R 2 It is methyl, R 3 It is isopropyl.

[0129] 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 was detected by thin-layer silica gel plate chromatography, and the fourth fraction was collected. The solvent was removed to give L1 (0.19 g, yield 20%) as an orange powder.

[0130] The structural verification data is as follows:

[0131] 1 H 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).

[0132] 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.

[0133] 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).

[0134] 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.

[0135] Example 2

[0136] The preparation of (4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-isopropylphenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine[L2] as shown in formula (II), wherein R 1 For hydrogen, R 2 It is isopropyl, R 3 It is isopropyl.

[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-isopropylbenzyl)acenaphthene (0.63 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 was detected by thin-layer silica gel plate analysis, and the fourth fraction was collected. The solvent was removed to give L2 (0.22 g, yield 23%) as an orange powder.

[0138] The structural verification data is as follows:

[0139] 1 H NMR (400MHz, CDCl3, TMS): δ7.65(d,J=8.0Hz,1H),7.49(d,J=8.0Hz,1H),7.48(s,2H),7.41(s,2H),7.27-7 .18(m,7H),7.11(d,J=12.0Hz,4H),6.93(d,J=12Hz,4H),6.86(t,J=8.0Hz,3H),6.60-6.57(m,5H),6.38(t ,J=8.0Hz,2H),5.81(d,J=4.0Hz,1H),5.66(s,2H),3.82(s,2H),3.23-3.19(m,2H),3.06-3.03(m,2H),2.8 7-2.79(m,1H),1.41(d,J=4.0Hz,12H),1.35(d,J=4.0Hz,6H),1.16(d,J=8.0Hz,6H),1.08(d,J=4.0Hz,6H).

[0140] 13 C NMR (CDCl3, 100MHz): δ163.9,162.4,147.4,145.9,143.9,141.9,140.1,139.7,138.2,136.0,133.0,132.2,132.1,129.9,129.8,129.7,1 28.7,128.6,128.1,127.9,127.8,127.0,126.3,126.1,125.6,124.3 ,123.2,121.9,121.6,52.4,33.7,28.8,28.4,24.4,24.3,23.9,22.7.

[0141] FT-IR (cm) -1 ):3497(w),3413(w),3057(w),3028(w),2960(m),2869(w),1659(ν(C=N),

[0142] m),1641(ν(C=N),m),1594(m),1493(m),1435(m),1342(m),1259(s),1086(m),1020(s),924(m),868(m),796(s),738(m),696(m).

[0143] Elemental analysis: C 71 H 71 Theoretical values ​​for N3 (966.37): C, 88.25; H, 7.41; N, 4.35. Experimental values: C, 87.96; H, 7.55; N, 4.11.

[0144] Example 3

[0145] The preparation of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-tert-butylphenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine[L3] as shown in formula (II), wherein R 1 For hydrogen, R 2 For tert-butyl, R 3 It is isopropyl.

[0146] 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-tert-butylbenzylimine)acenaphthene (0.65 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 detected 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 was detected by thin-layer silica gel plate analysis, and the fourth fraction was collected. The solvent was removed to give L3 (0.24 g, yield 25%) as an orange powder.

[0147] The structural verification data is as follows:

[0148] 1H NMR (400MHz, CDCl3, TMS): δ7.66(d,J=8.0Hz,1H),7.49(d,J=8.0Hz,1H),7.48(s,2H),7.41(s,2H),7.2 7-7.18(m,7H),7.11(d,J=12.0Hz,4H),7.01(s,2H),6.93(d,J=12.0Hz,4H),6.85(t,J=8.0Hz,1H),6.60 -6.55(m,5H),6.39(t,J=8.0Hz,2H),5.79(d,J=8.0Hz,1H),5.67(s,2H),3.83(s,2H),3.24-3.17(m,2H ),3.08-3.01(m,2H),1.41(d,J=4.0Hz,12H),1.35(d,J=4.0Hz,6H),1.19(s,9H),1.08(d,J=4.0Hz,6H).

[0149] 13 C NMR(CDCl3,100MHz): δ163.9,162.4,147.1,146.1,145.9,143.9,142.0,14 0.1,139.7,138.2,136.0,133.0,132.1,131.8,129.9,129.8,129.7,128.9, 128.7,128.6,128.1,127.9,127.8,127.0,126.1,125.5,125.4,124.3,123.2,121.9,121.6,53.7,53.6,52.5,34.6,31.6,28.8,28.4,24.4,23.9,22.7.

[0150] FT-IR (cm) -1 ):3487(w),3405(w),3081(w),3060(w),3025(w),2959(m),2868(w),1655(ν(C=N),m),1645(ν(C=N),m),1594( m),1494(m),1437(m),1339(m),1257(m),1192(m),1075(m),1013(s),927(m),873(m),781(m),762(m),699(s).

[0151] Elemental analysis: C 72 H 73 Theoretical values ​​of N3 (980.40): C, 88.21; H, 7.51; N, 4.29. Experimental values: C, 88.02; H, 7.85; N, 4.12.

[0152] Example 4

[0153] The preparation of (4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methoxyphenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine[L4] as shown in formula (II), wherein R 1 For hydrogen, R 2 It is a methoxy group, R 3 It is isopropyl.

[0154] 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-methoxybenzyl)acenaphthene (0.62 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 L4 (0.26 g, yield 27%) as an orange powder.

[0155] The structural verification data is as follows:

[0156] 1 H NMR (400MHz, CDCl3, TMS): δ7.68(d,J=8.0Hz,1H),7.52(d,J=8.0Hz,1H),7.48(s,2H),7.41( s,2H),7.28-7.19(m,7H),7.13(d,J=8.0Hz,4H),6.99-6.91(m,5H),6.60-6.55(m,7H),6.40( t,J=8.0Hz,2H),5.99(d,J=8.0Hz,1H),5.66(s,2H),3.83(s,2H),3.65(s,3H),3.22-3.18(m, 2H), 3.06-3.01 (m, 2H), 1.41 (d, J = 4.0Hz, 12H), 1.34 (d, J = 8.0Hz, 6H), 1.07 (d, J = 4.0Hz, 6H).

[0157] 13C NMR (CDCl3, 100MHz): δ164.5,162.4,155.8,145.8,143.3,141.5,140.1,139.7,138.2,135.9,133.9,133.0,132.0,129.8,129.7,1 28.8,128.7,128.3,127.9,127.0,126.3,125.7,124.4,123.2,121.9,121.5,114.0,55.4,52.4,29.8,28.7,28.4,24.4,23.9,22.7.

[0158] FT-IR (cm) -1 ):3497(w),3405(w),3060(w),3028(w),2960(m),2869(w),1663(ν(C=N),

[0159] m),1648(ν(C=N),m),1597(m),1494(m),1456(m),1435(s),1341(m),1298(w),1200 (m),1130(m),1096(m),1049(m),923(w),868(m),830(m),771(m),742(m),699(s).

[0160] Elemental analysis: C 69 H 67 Theoretical values ​​for N3O (954.32): C, 86.84; H, 7.08; N, 4.40. Experimental values: C, 86.52; H, 7.23; N, 4.23.

[0161] Example 5

[0162] The preparation of 4'-((1E,2E)-2-((2,6-bis(diphenylmethyl)-4-trifluoromethoxyphenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine[L5] as shown in formula (II), wherein R 1 For hydrogen, R 2 It is trifluoromethoxy, R 3 It is isopropyl.

[0163] 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-trifluoromethoxybenzyl)acenaphthene (0.67 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 was detected by thin-layer silica gel plate chromatography, and the fourth fraction was collected. The solvent was removed to give L5 (0.17 g, yield 17%) as an orange powder.

[0164] The structural verification data is as follows:

[0165] 1 H NMR (400MHz, CDCl3, TMS): δ7.69 (d, J = 8.0Hz, 1H), 7.53 (d, J = 8.0Hz, 1H), 7.49 (s, 2H), 7. 41(s,2H),7.30-7.20(m,7H),7.09(d,J=8.0Hz,4H),6.92-6.88(m,7H),6.62-6.56(m,5H) ,6.40(t,J=12Hz,2H),5.83(d,J=8.0Hz,1H),5.68(s,2H),3.84(s,2H),3.23-3.16(m,2H) ,3.08-3.01(m,2H),1.41(d,J=4.0Hz,12H),1.35(d,J=8.0Hz,6H),1.08(d,J=8.0Hz,6H).

[0166] 13 C NMR (CDCl3, 100MHz): δ164.4,162.2,148.0,145.6,142.7,140.8,140.2,139.8,138.4,135.9,134.6,133.1,131.9,129.8,129.6,128.8 ,128.6,128.4,128.3,128.2,127.3,127.0,126.6,126.0,124.2,123.4,122.0,121.6,121.3,52.2,28.8,28.4,24.4,23.9,23.4,22.7.

[0167] 19 F NMR (470MHz, CDCl3) δ -58.14.

[0168] FT-IR (cm) -1 ):3461(w),3383(w),3061(w),3032(w),2957(m),2932(w),2866(w),1667(ν(C=N),m),1647(ν(C=N),m),1620(m),1595( m),1494(w),1435(s),1338(w),1259(s),1214(m),1160(m),1099(m),1014(m),923(w),867(m),801(m),728(w),697(s).

[0169] Elemental analysis: C 69 H 64 Theoretical values ​​of F3N3O(1008.29): C, 82.19; H, 6.40; N, 4.17. Experimental values: C, 82.01; H, 6.75; N, 4.13.

[0170] Example 6

[0171] The preparation of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-chlorophenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine[L6] as shown in formula (II), wherein R 1 For hydrogen, R 2 For chlorine, R 3 It is isopropyl.

[0172] 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-chlorobenzyl)acenaphthene (0.62 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 was detected by thin-layer silica gel plate analysis, and the fourth fraction was collected. The solvent was removed to give L6 (0.19 g, yield 20%) as an orange powder.

[0173] The structural verification data is as follows:

[0174] 1H NMR (400MHz, CDCl3, TMS): δ7.69(d,J=8.0Hz,1H),7.54(d,J=8.0Hz,1H),7.49(s,2H),7.41( s,2H),7.30-7.22(m,7H),7.11(d,J=8.0Hz,4H),7.00(s,2H),6.94-6.91(m,5H),6.62-6.57( m,5H),6.41(t,J=8.0Hz,2H),5.96(d,J=8.0Hz,1H),5.65(s,2H),3.84(s,2H),3.22-3.16(m, 2H),3.08-3.01(m,2H),1.41(d,J=4.0Hz,12H),1.35(d,J=4.0Hz,6H),1.07(d,J=8.0Hz,6H).

[0175] 13 C NMR (CDCl3, 100MHz): δ164.2,162.3,148.0,145.7,142.7,141.0,140.2,139.8,138.4,135.9,134.8,133.0,131.9,129.8,129.6,12 9.0,128.8,128.7,128.4,128.3,128.1,127.2,127.0,126.6,126.0,124.4,123.4,122.0,121.5,52.3,28.8,28.4,24.4,23.9,22.7.

[0176] FT-IR (cm) -1 ):3473(w),3395(w),3060(w),3027(w),2958(m),2930(w),2866(w),1670(ν(C=N),m),1646(ν(C=N),m),1595(m),1494(m),1430 (s),1361(m),1340(m),1271(w),1242(m),1187(m),1110(w),1033(w),948(w),868(m),827(m),779(m),757(m),732(m),696(s).

[0177] Elemental analysis: C 68 H 64 Theoretical values ​​for ClN3 (958.73): C, 85.19; H, 6.73; N, 4.38. Experimental values: C, 85.01; H, 6.88; N, 4.30.

[0178] Example 7

[0179] The preparation of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-fluorophenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine [L7] as shown in formula (II), wherein R 1 For hydrogen, R 2 It is fluorine, R 3 It is isopropyl.

[0180] 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-fluorobenzyl)acenaphthene (0.61 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 was detected by thin-layer silica gel plate analysis, and the fourth fraction was collected. The solvent was removed to give L7 (0.18 g, yield 19%) as an orange powder.

[0181] The structural verification data is as follows:

[0182] 1 H NMR (400MHz, CDCl3, TMS): δ7.69(d,J=8.0Hz,1H),7.54(d,J=8.0Hz,1H),7.49(s,2H),7.41(s,2 H),7.30-7.19(m,7H),7.12(d,J=8.0Hz,4H),6.94-6.90(m,5H),6.76(d,J=12.0Hz,2H),6.62-6 .57(m,5H),6.41(t,J=8.0Hz,2H),5.95(d,J=4.0Hz,1H),5.67(s,2H),3.83(s,2H),3.23-3.16( m,2H),3.08-3.02(m,2H),1.41(d,J=8.0Hz,12H),1.35(d,J=8.0Hz,6H),1.07(d,J=8.0Hz,6H).

[0183] 13C NMR (CDCl3, 100MHz): δ164.6,162.3,145.7,142.9,141.0,140.2,139.8,138.3,135.9,134.8,134.7,133.0,132.0,129.9,129.6,128.8 ,128.5,128.4,128.2,128.1,127.2,126.9,126.6,125.9,124.3,123.3,122.0,121.6,115.4,115.2,52.3,28.8,28.4,24.4,23.9,22.7.

[0184] 19 F NMR (470MHz, CDCl3) δ-119.25.

[0185] FT-IR (cm) -1 ):3471(w),3395(w),3061(w),3024(w),2958(m),2935(w),2865(w),1669(ν(C=N),m),1645(ν(C=N),m),15 93(m),1495(m),1435(s),1341(m),1302(m),1260(m),1187(m),1095(s),1021(s),922(w),866(m),698(s).

[0186] Elemental analysis: C 68 H 64 FN3 (942.28) theoretical values: C, 86.68; H, 6.85; N, 4.46. Experimental values: C, 86.52; H, 6.91; N, 4.32.

[0187] Example 8

[0188] The preparation of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-nitrophenyl)imine)acenaphtheno-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine[L8] as shown in formula (II), wherein R 1 For hydrogen, R 2 It is nitro, R 3 It is isopropyl.

[0189] 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-nitrobenzeneimine)acenaphthene (0.63 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 detected 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 was detected by thin-layer silica gel plate analysis, and the fourth fraction was collected. The solvent was removed to give L8 (0.24 g, yield 25%) as an orange powder.

[0190] The structural verification data is as follows:

[0191] 1 H NMR (400MHz, CDCl3, TMS): δ7.94(s,2H),7.72(d,J=12.0Hz,1H),7.56(d,J=8.0Hz,1H),7.50(s,2H) ,7.41(s,2H),7.32-7.23(m,7H),7.11(d,J=8.0Hz,4H),6.95-6.89(m,5H),6.64(d,J=8.0Hz,1H),6. 59(t,J=8.0Hz,4H),6.41(t,J=8.0Hz,2H),5.84(d,J=8.0Hz,1H),5.72(s,2H),3.84(s,2H),3.22-3 .16(m,2H),3.09-3.02(m,2H),1.41(d,J=8.0Hz,12H),1.36(d,J=8.0Hz,6H),1.09(d,J=8.0Hz,6H).

[0192] 13 C NMR (CDCl3, 100MHz): δ163.6,162.1,155.3,145.4,144.3,142.0,140.2,139.9,138.6,135.8,134.6,133.0,131.8,129.8,129.5,12 9.0,128.8,128.7,128.4,128.0,127.5,127.0,126.3,124.3,123.8,123.6,122.0,121.5,52.4,28.9,28.4,27.0,24.4,23.9,22.7.

[0193] FT-IR (cm) -1):3478(w),3395(w),3061(w),3036(w),2958(m),2925(w),2865(w),1675(ν(C=N),m),1647(ν(C=N),m),1626(m),1591(m), 1514(s),1494(m),1435(m),1333(s),1253(m),1101(m),1026(m),917(m),870(m),802(m),759(m),734(m),800(s),697(s).

[0194] Elemental analysis: C 68 H 64 Theoretical values ​​for N4O2 (969.29): C, 84.26; H, 6.66; N, 5.78. Experimental values: C, 84.02; H, 6.85; N, 5.85.

[0195] Example 9

[0196] Prepare the [4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methylphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine]nickel bromide (II) [complex C1] shown in formula (I), wherein R 1 For hydrogen, R 2 It is methyl, R 3 X is isopropyl, and X is bromine.

[0197] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methylphenyl)imine)acenaphthenoyl-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.094 g, 0.10 mmol) in dichloromethane (20 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 (0.089 g), with a yield of 77%.

[0198] The structural verification data is as follows:

[0199] FT-IR (cm) -1):3447(w),3365(w),3058(w),3029(w),2960(m),2925(w),2867(w),1643(ν(C=N),m),1622(ν(C=N),m),15 99(m),1583(m),1494(m),1437(m),1338(m),1294(m),1193(m),1076(m),1041(m),871(m),770(m),702(s).

[0200] Elemental analysis: C 69 H 67 Theoretical values ​​for Br2N3Ni (1156.82): C, 71.64; H, 5.84; N, 3.63. Experimental values: C, 71.59; H, 5.97; N, 3.72.

[0201] Example 10

[0202] Prepare the [4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-isopropylphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine]nickel bromide (II) [complex C2] shown in formula (I), wherein R 1 For hydrogen, R 2 It is isopropyl, R 3 X is isopropyl, and X is bromine.

[0203] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-isopropylphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.097 g, 0.10 mmol) in dichloromethane (20 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 (0.093 g), with a yield of 78%.

[0204] The structural verification data is as follows:

[0205] FT-IR (cm) -1 ):3446(w),3364(w),3059(w),3029(w),2962(m),2868(w),1645(ν(C=N),

[0206] m),1622(ν(C=N),m),1600(m),1494(m),1438(m),1339(m),1294(m),1198(w),1125(w),1077(m),1041(m),871(m),770(m),747(m),702(s).

[0207] Elemental analysis: C 71 H 71 Theoretical values ​​for Br2N3Ni (1184.87): C, 71.97; H, 6.04; N, 3.55. Experimental values: C, 71.62; H, 6.13; N, 3.63.

[0208] Example 11

[0209] Prepare the [4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-tert-butylphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine]nickel bromide (II) [complex C3] shown in formula (I), wherein R 1 For hydrogen, R 2 For tert-butyl, R 3 X is isopropyl, and X is bromine.

[0210] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-tert-butylphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.098 g, 0.10 mmol) in dichloromethane (20 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 (0.092 g), with a yield of 77%.

[0211] The structural verification data is as follows:

[0212] FT-IR (cm) -1):3457(w),3374(w),3060(w),2964(m),2928(w),2904(w),2869(w),1647(ν(C=N),m),1622(ν(C=N),m),1599(m),1 494(m),1439(m),1363(w),1339(m),1263(m),1189(m),1075(m),1049(m),895(m),873(m),771(m),741(m),702(s).

[0213] Elemental analysis: C 72 H 73 Theoretical values ​​for Br2N3Ni (1198.90): C, 72.13; H, 6.14; N, 3.50. Experimental values: C, 71.81; H, 6.38; N, 3.55.

[0214] Example 12

[0215] Prepare the [4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methoxyphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine]nickel bromide (II) [complex C4] shown in formula (I), wherein R 1 For hydrogen, R 2 It is a methoxy group, R 3 X is isopropyl, and X is bromine.

[0216] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-methoxyphenyl)imine)acenaphthenoyl-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.095 g, 0.10 mmol) in dichloromethane (20 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 (0.090 g), with a yield of 77%.

[0217] The structural verification data is as follows:

[0218] FT-IR (cm) -1):3451(w),3369(w),3057(w),3022(w),2962(m),2928(w),2871(w),1645(ν(C=N),m),1621(ν(C=N),m),1598(m),1496( m),1459(m),1437(m),1339(m),1297(m),1198(m),1132(m),1053(m),957(w),872(m),828(m),770(m),745(m),701(s).

[0219] Elemental analysis: C 69 H 67 Theoretical values ​​for Br2N3NiO (1172.82): C, 70.66; H, 5.76; N, 3.58. Experimental values: C, 70.29; H, 6.05; N, 3.63.

[0220] Example 13

[0221] Prepare the [4'-((1E,2E)-2-((2,6-bis(diphenylmethyl)-4-trifluoromethoxyphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine]nickel bromide (II) [complex C5] as shown in formula (I), wherein R 1 For hydrogen, R 2 It is trifluoromethoxy, R 3 X is isopropyl, and X is bromine.

[0222] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-trifluoromethoxyphenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.101 g, 0.10 mmol) in dichloromethane (20 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 obtain a black solid (0.096 g), with a yield of 78%.

[0223] 19 F NMR (470MHz, CDCl3): δ-57.11.

[0224] FT-IR (cm) -1):3448(w),3372(w),3061(w),3027(w),2965(m),2935(w),2871(w),1645(ν(C=N),m),1624(ν(C=N),m),1602(m),1585( m),1458(w),1438(s),1341(w),1296(m),1258(s),1218(m),1169(m),1077(m),962(w),871(m),827(m),769(m),702(s).

[0225] Elemental analysis: C 69 H 64 Theoretical values ​​for Br2F3N3NiO (1226.79): C, 67.56; H, 5.26; N, 3.43. Experimental values: C, 67.32; H, 5.45; N, 3.52.

[0226] Example 14

[0227] Prepare the nickel bromide (II) [complex C6] of formula (I) shown, which contains R 1 For hydrogen, R 2 For chlorine, R 3 X is isopropyl, and X is bromine.

[0228] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-chlorophenyl)imine)acenaphthyl-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.096 g, 0.10 mmol) in dichloromethane (20 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 (0.091 g), with a yield of 78%.

[0229] FT-IR (cm) -1):3451(w),3378(w),3062(w),3032(w),2961(m),2930(w),2866(w),1647(ν(C=N),m),1620(ν(C=N),m),1600(m),1580( m),1491(m),1434(s),1340(m),1291(w),1222(w),1175(m),1040(m),894(w),870(m),828(m),770(m),740(m),700(s).

[0230] Elemental analysis: C 68 H 64 Theoretical values ​​for Br2ClN3Ni (1177.23): C, 69.38; H, 5.48; N, 3.57. Experimental values: C, 69.23; H, 5.60; N, 3.62.

[0231] Example 15

[0232] Prepare the nickel bromide (II) [complex C7] of formula (I) as shown in formula (I), which contains R 1 For hydrogen, R 2 It is fluorine, R 3 X is isopropyl, and X is bromine.

[0233] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-fluorophenyl)imine)acenaphthenoyl-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.094 g, 0.10 mmol) in dichloromethane (20 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 (0.093 g), with a yield of 79%.

[0234] 19 F NMR (470MHz, CDCl3): δ-42.24.

[0235] FT-IR (cm) -1):3504(w),3412(w),3062(w),3029(w),2963(m),2930(w),2904(w),2871(w),1647(ν(C=N),m),1620(ν(C= N),m),1589(m),1491(m),1437(s),1340(m),1294(m),1187(m),1074(m),1040(m),870(m),769(m),700(s).

[0236] Elemental analysis: C 68 H 64 Theoretical values ​​for Br2FN3Ni (1160.78): C, 70.36; H, 5.56; N, 3.62. Experimental values: C, 70.29; H, 5.72; N, 3.73.

[0237] Example 16

[0238] Prepare the [4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-nitrophenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine]nickel bromide (II) [complex C8] shown in formula (I), wherein R 1 For hydrogen, R 2 It is nitro, R 3 X is isopropyl, and X is bromine.

[0239] Under nitrogen protection, 0.9 equivalents of (DME)NiBr2 (0.028 g, 0.090 mmol) were added to a solution of 4'-((1E,2E)-2-((2,6-di(diphenylmethyl)-4-nitrophenyl)imine)acenaphthene-1-(2H)-imine)-3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4-amine (0.097 g, 0.10 mmol) in dichloromethane (20 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 (0.095 g), with a yield of 80%.

[0240] FT-IR (cm) -1):3454(w),3372(w),3060(w),3026(w),2961(m),2932(w),2871(w),1645(ν(C=N),m),1622(ν(C=N),m),1599(m),1579( m),1533(M),1492(m),1439(m),1341(s),1293(m),1080(m),1041(m),957(m),871(m),822(m),770(m),740(m),701(s).

[0241] Elemental analysis: C 68 H 64 Theoretical values ​​for Br2N4NiO2 (1187.79): C, 68.76; H, 5.43; N, 4.72. Experimental values: C, 68.59; H, 5.62; N, 4.81.

[0242] 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 1 As shown, it has an asymmetric structure, and the coordinating atoms exhibit a distorted tetrahedral geometry around the nickel center.

[0243] Example 17

[0244] Ethylene polymerization under pressure using C8 complex and MAO co-catalyst:

[0245] 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, 1.4 mL of a 1.46 mol / L toluene solution of co-catalyst MAO, 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.

[0246] Polymerization activity: 6.7 × 10 6 g·mol -1 (Ni)·h-1 polymer melting point T m =92.4℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =20.1×10 5 g·mol -1 PDI = 2.3 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0247] Example 18

[0248] Ethylene polymerization under pressure using C8 complex and MMAO co-catalyst:

[0249] 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 containing 1 μmol of catalyst C8, 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 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.

[0250] Polymerization activity: 4.7 × 10 6 g·mol -1 (Ni)·h -1 polymer melting point T m =88.8℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =17.0×10 5 g·mol -1 PDI = 2.0 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0251] Example 19

[0252] Ethylene polymerization under pressure using C8 complex and Me2AlCl as co-catalysts:

[0253] 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, 0.5 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, 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.

[0254] Polymerization activity: 6.4 × 10 6 g·mol -1 (Ni)·h -1 polymer melting point T m =93.4℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =4.6×10 5 g·mol -1 PDI = 1.9 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0255] Example 20

[0256] Ethylene polymerization under pressure using C8 complex and AlMe3 co-catalyst:

[0257] 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, 0.25 mL of a 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 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.

[0258] Polymerization activity: 8.0 × 10 6 g·mol -1 (Ni)·h -1 polymer melting point T m =100.2℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =17.1×10 5 g·mol -1 PDI = 2.7 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0259] 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. After 2000 signal accumulations, the signal peak shifts were between 10-40 ppm, indicating shifts in methyl, methylene, and methine groups. This confirms that the obtained polymer is branched polyethylene with a moderate degree of branching (68B / 1000C) and no long branches (see details). Figure 2 ).

[0260] Example 21

[0261] Ethylene polymerization under pressure using C8 complex and AlMe3 co-catalyst:

[0262] 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 containing 2 μmol of catalyst C8, 0.5 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.

[0263] Polymerization activity: 3.2 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =83.2℃(T) m(The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =5.8×10 5 g·mol -1 PDI = 2.0 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0264] Example 22

[0265] Ethylene polymerization under pressure using C8 complex and AlMe3 co-catalyst:

[0266] a) Basically the same as Example 20, except that the polymerization temperature is 20°C. Polymerization activity: 5.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =100.5℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =13.0×10 5 g·mol -1 PDI = 2.2 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0267] b) Basically the same as Example 20, except that the polymerization temperature is 40°C. Polymerization activity: 7.3 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =63.4℃, polymer molecular weight M w =16.3×10 5 g·mol -1 PDI = 2.1.

[0268] c) Basically the same as Example 20, except that the polymerization temperature is 50°C. Polymerization activity: 7.0 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =48.0℃, polymer molecular weight M w =15.6×10 5 g·mol -1 PDI = 2.3.

[0269] d) Basically the same as Example 20, except that the polymerization temperature is 60℃. Polymerization activity: 5.2 × 10⁻⁶ 6 g·mol -1(Ni)·h -1 polymer melting point T m =42.6℃, polymer molecular weight M w =12.3×10 5 g·mol -1 PDI = 2.3.

[0270] e) Basically the same as Example 20, except that the polymerization temperature is 80°C. Polymerization activity: 2.8 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =30.5℃, polymer molecular weight M w =9.9×10 5 g·mol -1 PDI = 2.1.

[0271] f) Basically the same as Example 20, except that: the amount of co-catalyst used is 0.375 mL of AlMe3 (2.00 mol / L, n-hexane solution), making Al / Ni = 750:1. Polymerization activity: 5.6 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =89.8℃, polymer molecular weight M w =18.2×10 5 g·mol -1 PDI = 2.1.

[0272] g) Basically the same as Example 20, except that: the amount of co-catalyst used is 0.5 mL of AlMe3 (2.00 mol / L, n-hexane solution), making Al / Ni = 1000:1. Polymerization activity: 5.3 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =93.1℃, polymer molecular weight M w =26.9×10 5 g·mol -1 PDI = 1.9.

[0273] h) Basically the same as Example 20, except that: the amount of co-catalyst used is 0.75 mL of AlMe3 (2.00 mol / L, n-hexane solution), making Al / Ni = 1500:1. Polymerization activity: 4.7 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m=70.7℃, polymer molecular weight M w =22.4×10 5 g·mol -1 PDI = 2.2.

[0274] i) Basically the same as Example 20, except that: the amount of co-catalyst used is 1.0 mL of AlMe3 (2.00 mol / L, n-hexane solution), making Al / Ni = 2000:1. Polymerization activity: 4.4 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 Polymer T m =68.9℃, polymer molecular weight M w =8.1×10 5 g·mol -1 PDI = 2.2.

[0275] j) Basically the same as Example 20, except that the ethylene pressure is 5 atm. Polymerization activity: 2.1 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =75.4℃, polymer molecular weight M w =2.2×10 5 g·mol -1 PDI = 2.5.

[0276] Example 23

[0277] Ethylene polymerization under pressure using complex C1 and AlMe3 as co-catalysts:

[0278] Basically the same as Example 20, except that the main catalyst is C1. Polymerization activity: 10.6 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =69.4℃, polymer molecular weight M w =13.5×10 5 g·mol -1 PDI = 2.2.

[0279] Example 24

[0280] Ethylene polymerization under pressure using complex C2 and AlMe3 as co-catalysts:

[0281] The process is basically the same as in Example 20, except that the main catalyst is C2. Polymerization activity: 10.7 × 10⁻⁶ 6 g·mol -1(Ni)·h -1 polymer melting point T m =71.7℃, polymer molecular weight M w =15.3×10 5 g·mol -1 PDI = 2.1.

[0282] Example 25

[0283] Ethylene polymerization under pressure using C3 complex and AlMe3 co-catalyst:

[0284] The process is basically the same as in Example 20, except that the main catalyst is C3. Polymerization activity: 12.1 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =66.9℃, polymer molecular weight M w =17.2×10 5 g·mol -1 PDI = 1.9.

[0285] 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 (121B / 1000C) and a long-chain proportion of 6.7% (see details). Figure 3 ).

[0286] Example 26

[0287] Ethylene polymerization under pressure using C4 complex and AlMe3 co-catalyst:

[0288] Basically the same as Example 20, except that the main catalyst is C4. Polymerization activity: 8.1 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =88.6℃, polymer molecular weight M w =6.8×10 5 g·mol -1 PDI = 2.0.

[0289] Example 27

[0290] Ethylene polymerization under pressure using C5 complex and AlMe3 co-catalyst:

[0291] The process is basically the same as in Example 20, except that the main catalyst is C5. Polymerization activity: 2.3 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =84.4℃, polymer molecular weight M w =17.0×10 5 g·mol -1 PDI = 1.9.

[0292] Example 28

[0293] Ethylene polymerization under pressure using C6 complex and AlMe3 co-catalyst:

[0294] The process is basically the same as in Example 20, except that the main catalyst is C6. Polymerization activity: 5.1 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =82.0℃, polymer molecular weight M w =7.2×10 5 g·mol -1 PDI = 1.9.

[0295] Example 29

[0296] Ethylene polymerization under pressure using C7 complex and AlMe3 co-catalyst:

[0297] Basically the same as Example 20, except that the main catalyst is C7. Polymerization activity: 8.9 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =69.3℃, polymer molecular weight M w =13.5×10 5 g·mol -1 PDI = 2.3.

[0298] Example 30

[0299] Ethylene polymerization under pressure using complex C1 and Me2AlCl as co-catalysts:

[0300] 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 (2 μmol), 1 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.

[0301] Polymerization activity: 11.2 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =49.1℃(T) m (The melting temperature of the polymer is obtained by DSC testing), and the polymer molecular weight M is... w =10.9×10 5 g·mol -1 PDI = 2.2 (M w (This represents the mass-average molecular weight of the polymer, obtained through heated GPC testing).

[0302] The obtained polyethylene was subjected to mechanical tensile property tests. Five tests were conducted, and the average value was taken. The tensile strength was 3.67 MPa, and the elongation at break was 343% (see the mechanical property test spectrum for details). Figure 6 ).

[0303] Example 31

[0304] Ethylene polymerization under pressure using complex C2 and Me2AlCl as co-catalysts:

[0305] The process is basically the same as in Example 30, except that the main catalyst is C2. Polymerization activity: 11.2 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =48.3℃, polymer molecular weight M w =13.5×10 5 g·mol -1PDI = 1.9. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 3.45 MPa, and the elongation at break was 263% (see the mechanical property test spectrum for details). Figure 6 ).

[0306] Example 32

[0307] Ethylene polymerization under pressure using complex C3 and Me2AlCl as co-catalysts:

[0308] The process is basically the same as in Example 30, except that the main catalyst is C3. Polymerization activity: 14.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =93.0℃, polymer molecular weight M w =18.9×10 5 g·mol -1 PDI = 2.2.

[0309] 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 (156B / 1000C) and a long-chain proportion of 7.0% (see details). Figure 4 ).

[0310] Example 33

[0311] Ethylene polymerization under pressure using C4 complex and Me2AlCl as co-catalysts:

[0312] The process is basically the same as in Example 30, except that the main catalyst is C4. Polymerization activity: 13.5 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =65.1℃, polymer molecular weight M w =15.4×10 5 g·mol -1 PDI = 2.4.

[0313] Example 34

[0314] Ethylene polymerization under pressure using complex C5 and Me2AlCl as co-catalysts:

[0315] The process is basically the same as in Example 30, except that the main catalyst is C5. Polymerization activity: 10.0 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =51.6℃, polymer molecular weight M w =8.2×10 5 g·mol -1 PDI = 2.2.

[0316] Example 35

[0317] Ethylene polymerization under pressure using C6 complex and Me2AlCl as co-catalysts:

[0318] The process is basically the same as in Example 30, except that the main catalyst is C6. Polymerization activity: 12.6 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =44.9℃, polymer molecular weight M w =9.2×10 5 g·mol -1 PDI = 2.2. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 3.60 MPa, and the elongation at break was 410% (see the mechanical property test spectrum for details). Figure 6 ).

[0319] Example 36

[0320] Ethylene polymerization under pressure using C7 complex and Me2AlCl as co-catalysts:

[0321] The process is basically the same as in Example 30, except that the main catalyst is C7. Polymerization activity: 12.8 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =41.9℃, polymer molecular weight M w =11.2×10 5 g·mol -1 PDI = 2.2. The obtained polyethylene was subjected to mechanical tensile property testing. Five tests were conducted, and the average value was taken. The tensile strength was 3.67 MPa, and the elongation at break was 343% (see the mechanical property test spectrum for details). Figure 6 ).

[0322] Example 37

[0323] Ethylene polymerization under pressure using C8 complex and Me2AlCl as co-catalysts:

[0324] The process is basically the same as in Example 30, except that the main catalyst is C8. Polymerization activity: 17.1 × 10⁻⁶ 6 g·mol -1 (Ni)·h -1 polymer melting point T m =41.9℃, polymer molecular weight M w =10.4×10 5 g·mol -1 PDI = 2.4.

[0325] 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 (146B / 1000C) and a long-chain proportion of 6.6% (see details). Figure 5 ).

[0326] The obtained polyethylene was subjected to mechanical tensile property tests. Five tests were conducted, and the average value was taken. The tensile strength was 4.81 MPa, and the elongation at break was 245% (see the mechanical property test spectrum for details). Figure 6 The obtained polymer was subjected to stress-strain recovery tests, and the elastic recovery rate was 80% (see mechanical property test spectrum for details). Figure 7 ).

[0327] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0328] 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 acenaphthene-α-diimine nickel complex containing an amino group, having the structure shown in formula (I): Formula (I) in, R 1 Same or different, R 1 Selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, or C3-C10 cycloalkyl; 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 Same or different, R 3 Selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C10 cycloalkyl; X is the same or different, selected from halogens.

2. The nickel complex according to claim 1, wherein, The R 1 Same or different, selected from hydrogen or C1-C6 alkyl; 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 or -O-C3-C10 cycloalkyl; The R 3 Same or different, selected from C1 to C6 alkyl groups; The X may be the same or different, and is selected from fluorine, chlorine or bromine.

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

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

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

6. The nickel complex according to claim 4, wherein, The R 1 Same or different, selected from hydrogen or C1-C4 alkyl; The R 2 Selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 fluoroalkoxy, fluorine, chlorine, bromine or nitro; The R 3 Same or different, selected from C2 to C4 alkyl groups; X is selected from chlorine or bromine.

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

8. A method for preparing the amine-containing asymmetric acenaphthene α-diimine nickel complex according to any one of claims 1-7, wherein, The preparation method includes the following steps: S1: The acenaphthene monoketone of formula (III) undergoes a ketamine condensation reaction with benzidine of formula (IV) to obtain a ligand compound of formula (II); and S2: The ligand compound undergoes a complexation reaction with a nickel-containing reagent to obtain the nickel complex; Among them, R 1 R 2 and R 3 As defined in any one of claims 1-7.

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

10. The preparation 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 catalyst. In step S2, the ligand compound and the nickel-containing reagent undergo a complexation reaction in a second organic solvent.

12. The preparation method according to claim 11, wherein, The first organic solvent is selected from aromatic organic solvents.

13. The preparation method according to claim 12, wherein, The first organic solvent is selected from toluene.

14. The preparation method according to claim 11, wherein, The catalyst is selected from p-toluenesulfonic acid.

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

16. The preparation method according to claim 11, wherein, The ketamine condensation reaction was carried out under reflux for 6–24 h.

17. The preparation method according to claim 11, wherein, The second organic solvent is selected from one or more of haloalkanes and alcohols.

18. The preparation method according to claim 17, wherein, The second organic solvent is selected from one or more of dichloromethane and ethanol.

19. The preparation method according to claim 11, wherein, The molar ratio of the ligand compound to the nickel-containing reagent is 1 to 2:

1.

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

21. An asymmetric acenaphthene α-diimine ligand compound containing an amino group, having the structure shown in formula (II): Equation (II) in, R 1 R 2 and R 3 As defined in any one of claims 1-7.

22. The ligand compound according to claim 21, wherein, The ligand compound is selected from one of the following:

23. A catalyst composition comprising a main catalyst and optionally a co-catalyst, wherein, The main catalyst is the amine-containing asymmetric acenaphthene α-diimine nickel complex according to any one of claims 1-7.

24. The catalyst composition according to claim 23, wherein, The cocatalyst is selected from one or more of aluminoxane cocatalysts, alkylaluminum cocatalysts, and alkylaluminum chloride cocatalysts.

25. The catalyst composition according to claim 24, 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.

26. The catalyst composition according to claim 25, wherein, When the cocatalyst is selected from methylaluminoxane, the molar ratio of metallic Al to the central metallic Ni of the 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 nickel complex is 1000-3000:

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

1.

27. Use of the amine-containing asymmetric acenaphthene α-diimine nickel complex according to any one of claims 1-7, or the catalyst composition according to any one of claims 23-26, in the catalytic polymerization of olefins.

28. The use according to claim 27, wherein the use is in the catalytic polymerization of ethylene.

29. The use according to claim 28, wherein, The ethylene polymerization is either homopolymerization of ethylene or copolymerization of ethylene with α-olefins.

30. The use according to claim 29, wherein, The α-olefin is a C3 to C20 α-olefin.

31. An olefin polymerization method, using the amine-containing asymmetric acenaphthene α-diimine nickel complex according to any one of claims 1-7, or the catalyst composition according to any one of claims 23-26 as a catalyst.

32. The olefin polymerization method according to claim 31, wherein, The olefin polymerization is ethylene polymerization.

33. The olefin polymerization method according to claim 32, wherein, The ethylene polymerization is either homopolymerization of ethylene or copolymerization of ethylene with α-olefins.

34. The olefin polymerization method according to claim 33, wherein, The α-olefin is a C3 to C20 α-olefin.

35. A method for preparing polyethylene, wherein the amine-containing asymmetric acenaphthene α-diimine nickel complex according to any one of claims 1-7, or the catalyst composition according to any one of claims 23-26, is used as a catalyst to polymerize ethylene under its catalytic action to prepare polyethylene.

36. The preparation method according to claim 35, wherein, The polymerization reaction is carried out at a temperature of 20–80°C.

37. The preparation method according to claim 35, wherein, The polymerization reaction takes 5 to 100 minutes.

38. The preparation method according to claim 35, wherein, The polymerization reaction is carried out at a pressure of 0.3–20 atm.

39. The preparation method according to claim 35, wherein, The polymerization reaction is carried out in a third organic solvent, which is selected from one or more of toluene, xylene, dichloromethane, tetrahydrofuran, n-hexane, or cyclohexane.

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