Photoresponsive mononuclear nickel / palladium complex for preparing ultra-high molecular weight polyethylene as well as preparation method and application of photoresponsive mononuclear nickel / palladium complex

Abstract

The invention provides a light response type mononuclear nickel / palladium complex for preparing ultra-high molecular weight polyethylene and a preparation method and application of the light response type mononuclear nickel / palladium complex, the structural formula of the light response type mononuclear nickel / palladium complex is as follows: # imgabs0 #. The light response type nickel / palladium complex provided by the invention has a rigid diphenylethylene skeleton and is converted from trans-configuration (E) to cis-configuration (Z) under irradiation of 365nm ultraviolet light; under the irradiation of 405nm ultraviolet light, a cis-configuration (Z) is converted into a trans-configuration (E). Therefore, the ratio of the E-type configuration to the Z-type configuration in the photoresponse type nickel complex can be accurately regulated and controlled by utilizing ultraviolet irradiation, and the photoresponse type nickel complex is used as a catalyst to regulate the reaction rate of two different sites in the olefin polymerization process, so that the molecular weight of a polyolefin material and the insertion rate of a polar monomer are regulated and controlled. The molecular weight distribution of the obtained ultrahigh molecular weight polyethylene is 1.60-2.57, and the molecular weight is 632-1184 * 10 < 4 > g.mol <-1 >. The catalyst has ultrahigh catalytic activity, can be used for producing high-performance polyethylene, can greatly reduce the production cost of the catalyst, and has great industrial application potential.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to a light-responsive mononuclear nickel / palladium complex for preparing ultra-high molecular weight polyethylene, and a preparation method and application thereof. Background Art

[0002] The iterative update of olefin polymerization catalysts has injected more diversified product types and more outstanding practical value into polyolefin materials. Polyolefins cover five categories: high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE) and polypropylene (PP). Among them, ultra-high molecular weight polyethylene has a series of characteristics such as chemical corrosion resistance, wear resistance, impact resistance, and self-lubrication. At present, it has been widely used in many industries such as biomedicine, military equipment, and diaphragm batteries.

[0003] Currently, 70% of the world's UHMWPE is still produced industrially using supported ZN catalysts. However, such catalysts tend to produce polymers with ultra-low branching (less than one in 100,000) and wide molecular weight distribution (about 5 to 20), which makes it extremely difficult to process them using traditional processing techniques. As for metallocene catalysts, not only are the co-catalysts expensive, but metallocene complexes that can be used to synthesize ultra-high molecular weight polyethylene are also relatively scarce.

[0004] In view of this, the researchers focused their research on non-macromolecule late transition catalysts. With the careful design and synthesis of ligands, the polymer structure can be precisely controlled to obtain ultra-high molecular weight polyethylene with a high molecular weight and a narrow molecular weight distribution. In recent years, the research groups of Jian Zhongbao, Dai Shengyu and Sun Wenhua have successfully designed related results that can be used to prepare ultra-high molecular weight polyethylene (Mw = 126 ~ 467 × 10 4 g·mol -1 ) (J. Catal., 2020, 390, 30, CN111548285A; Organometallics, 2022, 41, 124, CN114349658A; Polym. Chem., 2023, 14, 183; Polymer, 2024, 293, 126690).

[0005] In addition to the electronic effect and steric effect of the catalyst ligands mentioned in the above articles, there are also secondary coordination effects and weak intermolecular interaction effects to implement internal control strategies for the catalyst itself. However, this approach has led to the increasing complexity of the synthesis of new catalysts in recent years, and the synthesized catalysts often only show a single catalytic performance. In addition to internal control methods, introducing stimulus-responsive structural units into the skeleton of polymerization catalysts is also a feasible path, that is, in the process of polymerization, with the help of external stimulus factors (such as redox, electrochemical processes, mechanochemical control methods, acid / base environment and light, etc.), the original single catalyst precursor is driven to derive one or more catalytically active species. In view of the differences in the polymerization activity exhibited by different catalytic active centers, this can achieve effective regulation of the polymerization process.

[0006] Among various external stimulation methods, light has become an extremely ideal external stimulation source because of its high versatility, environmental friendliness and ease of operation. Therefore, the use of light to regulate the polymerization process and the microstructure of the polymer is of great research value and attraction. In recent years, some researchers have tried to introduce azobenzene functional groups into the catalyst system, relying on the photoinduced isomerization characteristics of azobenzene functional groups to achieve the regulation of the microstructure of polyolefin materials (Macromolecules, 2019, 52, 5646; Angew. Chem. Int. Ed. 2021, 60, 22195; Chin. J. Chem. 2022, 40, 2919; Chin. Chem. Lett., 2024, 35, 109534). However, due to the relatively high repulsive energy between the two phenyl groups in azobenzene compounds, the stability of its cis structure is poor, and it will gradually transform into a trans structure even at room temperature. As a result, it is difficult to precisely control the fine structure of polyethylene materials by adjusting the cis-trans structure ratio of the catalyst with azobenzene functional group as a light switch under high temperature environment. In response to this problem, in 2024, the research group of Chen Changle and the research group of Jiang Hui (Sci.China Chem.2024, https: / / doi.org / 10.1007 / s11426-024-2201-6 ) innovatively introduced a rigid stilbene skeleton into the catalyst system, and with the help of the effect of light on the catalyst, successfully achieved the regulation of the polymerization process and obtained polymers with different properties. Unfortunately, there are very few copolymerization products with enolates and enoic acids in the obtained polymers. The non-polar nature of polyethylene, while giving it chemical stability, also limits its wider industrial application. The direct coordination copolymerization of ethylene with polar monomers does not require harsh experimental conditions, but has only achieved limited success so far.

[0007] In summary, given that the catalysts in the prior art that use azobenzene functional groups as photoswitches have the problem of unstable cis structures, it is difficult to control the fine structure of polyethylene materials by regulating the cis-trans structure ratio under high temperature conditions. In addition, there is an urgent need to improve the activity of catalysts to produce high-performance high-end polyolefins. Therefore, it has become a top priority to develop a class of light-responsive catalysts for the catalytic synthesis of functionalized high-end polyethylene. Summary of the invention

[0008] In view of the fact that the catalyst with azobenzene functional group as light switch in the prior art has unstable cis structure, and there is an urgent need to improve the activity of the catalyst to produce high-performance high-end polyolefins, the present invention provides a temperature-insensitive rigid diphenylethylene photoresponsive mononuclear imine nickel / palladium complex. The photoresponsive nickel complex can stably exist under high temperature conditions of 120°C; it can undergo configuration conversion under ultraviolet light of two different wavelengths, and transform from trans configuration (E) to cis configuration (Z) under 365nm ultraviolet light, and transform from cis configuration (Z) to trans configuration (E) under 405nm ultraviolet light. It can be seen that the ratio between the E-configuration and the Z-configuration of the photoresponsive nickel complex can be accurately regulated by ultraviolet light irradiation. When this photoresponsive nickel complex is used as a catalyst, the reaction rate in the olefin polymerization process can be adjusted, thereby achieving effective regulation of the molecular weight of the polyolefin material and the insertion rate of the polar monomer.

[0009] Moreover, the complex of the present application has high catalytic activity in catalyzing ethylene polymerization and good thermal stability; the molecular weight distribution of the obtained ultra-high molecular weight polyethylene is 1.60-2.57, and the molecular weight is 632-1184×10 4 g·mol -1 , and has good physical and mechanical properties, the elastic recovery rate of the product is as high as 92%.

[0010] The technical solution provided by the present invention is specifically as follows:

[0011] In a first aspect, the present invention provides imine nickel / palladium complexes having chemical structures shown in formulas E-(I), Z-(I), E-(II) and Z-(II):

[0012]

[0013] Where R 1 is one of hydrogen, cyano, OCH2CH2OCH3, substituted phenyl, R 2 is one of hydrogen, halogen, and alkoxy; M is one of metal Ni or Pd.

[0014] Preferably, the α-diimine nickel / palladium complex of the chemical structure shown in formula E-(I) includes at least one of E-(I)-1 to E-(I)-5, the pyridine imine nickel / palladium complex of the chemical structure shown in formula E-(II) includes at least one of E-(II)-1 to E-(II)-3, the α-diimine nickel / palladium complex of the chemical structure shown in formula Z-(I) includes at least one of Z-(I)-1 to Z-(I)-5, and the pyridine imine nickel / palladium complex of the chemical structure shown in formula Z-(II) includes at least one of Z-(II)-1 to Z-(II)-3:

[0015]

[0016] In a second aspect, the present invention provides a method for synthesizing an α-diimine nickel / palladium complex having a chemical structure shown in Formula E-(I) and Z-(I), comprising:

[0017] The compound represented by formula E / Z-1 and compound 5 are subjected to Suzuki coupling reaction at 80-120°C under the catalysis of a second catalyst to generate an aniline compound represented by formula E / Z-2. The compound represented by formula E / Z-2 and compound 6 are subjected to Suzuki coupling reaction at 80-120°C under the catalysis of a second catalyst to generate an aniline compound represented by formula E / Z-3. Compound 7 and the aniline compound represented by formula E / Z-3 are subjected to condensation reaction at 80-120°C under the catalysis of a third catalyst to generate an α-diimine compound represented by formula E / Z-4.

[0018] The α-diimine compound represented by formula E / Z-4 is reacted with (DME)NiBr2 or (COD)PdMeCl at 0-45° C. to generate an α-diimine nickel / palladium complex having a chemical structure represented by formula E-(I) and Z-(I);

[0019]

[0020]

[0021] R 1 is one of hydrogen, cyano, OCH2CH2OCH3, substituted phenyl, R 2 It is one of hydrogen, halogen and alkoxy.

[0022] The second catalyst is tetrakis(triphenylphosphine)palladium or 1,1'-bis(diphenylphosphino)ferrocenepalladium(II) dichloride;

[0023] The third catalyst is zinc dichloride or p-toluenesulfonic acid.

[0024] In the method for synthesizing a diimine compound having a chemical structure shown in formula E / Z-3 provided by the present invention, the molar ratio of formula E / Z-1 to compound 5 is (1-2):1; the molar ratio of formula E / Z-2 to compound 6 (2,6-diisopropyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)aniline) is (1-2):1; the molar ratio of compound 7 to formula E / Z-3 is (1-2):1.

[0025] In a third aspect, the present invention provides a method for synthesizing a pyridine imine nickel / palladium complex having a chemical structure shown in Formula E-(II) and Z-(II), comprising:

[0026] Compound 9 and Formula E / Z-3 are subjected to a condensation reaction at 80 to 120° C. under the catalysis of a fourth catalyst to generate a pyridine imine compound represented by Formula E / Z-8;

[0027] The pyridine imine compound represented by formula E / Z-8 is reacted with (DME)NiBr2 or (COD)PdMeCl at 0-45°C to generate a pyridine imine nickel / palladium complex having a chemical structure represented by formula E-(II) and Z-(II);

[0028] The reaction route is as follows:

[0029]

[0030] Among them, R 1 It is one of hydrogen, cyano, OCH2CH2OCH3, and substituted phenyl.

[0031] The fourth catalyst is zinc dichloride or p-toluenesulfonic acid.

[0032] In the synthesis method of the pyridine imine compound having the chemical structure shown in Formula E / Z-8 provided by the present invention, the molar ratio of the compound 9 to the compound E / Z-3 is (1-2):1.

[0033] In the synthesis method of the α-diimine nickel / palladium complex having the formula E-(I) / Z-(I) and the chemical structure shown in the present invention, the reaction time of the α-diimine compound and (DME)NiBr2 or (COD)PdMeCl is 1 to 50 hours.

[0034] In the synthesis method of the pyridine imine nickel / palladium complex having the chemical structure shown in Formula E-(II) and Z-(II) provided by the present invention, the molar ratio of Formula E / Z-4 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1-6); the molar ratio of Formula E / Z-8 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1-6).

[0035] In the synthesis method of the imine nickel / palladium complex of the chemical structure shown in E-(I), Z-(I), E-(II) and Z-(II) provided by the present invention, the imine compound shown in formula E / Z-4 or E / Z-8 reacts with (DME)NiBr2 or (COD)PdMeCl in an organic solvent, and the organic solvent is an organic solvent well known to those skilled in the art, preferably a halogenated alkane, more preferably dichloromethane. The molar ratio of the imine compound to (DME)NiBr2 is 1:(0.1-6). In a specific embodiment, the molar ratio of the imine compound to (DME)NiBr2 or (COD)PdMeCl is 1:(1-3). Preferably, the reaction is carried out at 0°C to 38°C, and the reaction time is 1-50h; in a specific embodiment, the reaction time is 12-24h.

[0036] The invention also provides the use of imine nickel / palladium complexes with chemical structures shown by E-(I), Z-(I), E-(II) and Z-(II) in the synthesis of polyolefins.

[0037] In some embodiments provided by the present invention, the method further comprises: before adding a catalytic amount of the photoresponsive nickel / palladium complex to the olefin polymerization system, irradiating the photoresponsive nickel / palladium complex with ultraviolet light.

[0038] In some embodiments provided by the present invention, the wavelength of the ultraviolet light is 365nm or 405nm.

[0039] In some embodiments provided by the present invention, the application includes: contacting a terminal olefinic compound with an imine nickel / palladium complex having a chemical structure represented by E-(I), Z-(I), E-(II) and Z-(II), and an alkyl aluminum reagent, and the terminal olefinic compound undergoes a homopolymerization reaction. In this application, the homopolymerization reaction is carried out in an organic solvent, and after the compounds represented by formulas E-(I) and Z-(I) are irradiated with ultraviolet light, they are used as catalysts to catalyze the polymerization of ethylene to obtain a polyethylene product; the wavelength of the ultraviolet light is 365nm or 405nm, and the amount of the complex used in this application is 5 to 40μmol·L -1 The temperature of the homopolymerization reaction is 0℃~150℃, the pressure is 0.1~2.0MPa, and the reaction time is 0.05~3.00h.

[0040] In the application of the present invention, the light response behavior of the E-type catalyst is first explored. In the ultraviolet absorption spectrum, under the irradiation of a 365nm ultraviolet lamp, the E-type catalyst has a double peak at about 350nm, which is the characteristic absorption peak of rigid diphenylethylene. As time goes by, the absorption intensity of the double peak weakens. There are two isosbestic points, indicating that part of the E-type is converted to the Z-type. Under the irradiation of a 405nm ultraviolet lamp, the Z-type catalyst has only one peak at about 350nm. As time goes by, a double peak appears, and the absorption intensity of the double peak is enhanced. There are two isosbestic points, indicating that part of the Z-type is converted to the E-type. According to the results of the ultraviolet-visible spectrum, the illumination time is determined.

[0041] In some embodiments provided by the present invention, the application includes: contacting a terminal olefin-containing compound and a polar monomer with an α-diimine nickel / palladium complex having a chemical structure shown in formula E-(I) and an alkyl aluminum reagent, and copolymerizing the terminal olefin-containing compound with the polar monomer; the polar monomer refers to an olefin containing a heteroatom, including at least one of 10-undecenoic acid methyl ester, methyl acrylate, vinyltrimethoxysilane, propylene acetate, methyl norbornane methyl ester, 6-chloro-1-hexene, 10-undecenol, etc. In this application, the temperature of the copolymerization reaction is 0 to 50°C, the pressure of the copolymerization reaction is 0.1 to 1.0 MPa, and the reaction time is 0.05 to 3.00 h. The concentration of the α-diimine nickel / palladium complex is 0.2 to 0.4 μmol·mL -1 , the monomer concentration is 0.1~3.0M.

[0042] Preferably, in the above application, the compound containing a terminal olefin group is an olefin, more preferably ethylene, and the alkyl aluminum reagent includes one or more of MAO, MMAO, AlMe3, AlEtCl2, AlEt2Cl, AlEt3; and the sodium borate is NaBArF.

[0043] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0044] 1. The photoresponsive nickel complex can stably exist under high temperature conditions of 120°C; it can undergo configuration conversion under the irradiation of two different wavelengths of ultraviolet light, from the trans configuration (E) to the cis configuration (Z) under 365nm ultraviolet light, and from the cis configuration (Z) to the trans configuration (E) under 405nm ultraviolet light. It can be seen that the ratio between the E-configuration and the Z-configuration of the photoresponsive nickel complex can be precisely controlled by ultraviolet light irradiation. When this photoresponsive nickel complex is used as a catalyst, the reaction rate in the olefin polymerization process can be adjusted, thereby achieving effective control of the molecular weight of the polyolefin material and the insertion rate of the polar monomer.

[0045] 2. The polymer obtained by catalyzing ethylene homopolymerization with the photoresponsive nickel / palladium complex provided by the present invention is an elastomer with ultrahigh molecular weight. The catalyst has high catalytic activity in catalyzing ethylene polymerization and good thermal stability. The molecular weight distribution of the obtained ultrahigh molecular weight polyethylene is 1.60-2.57, and the molecular weight is 632-1184×10 4 g·mol -1 , and has good physical and mechanical properties, and the elastic recovery rate of the product is as high as 92%. The Z-type configuration of the light-responsive nickel / palladium complex provided by the present invention can make the polyethylene have fewer branches, and the E-type configuration can make the polyethylene have more branches; the Z-type configuration can make the molecular weight of the polyethylene larger, and the E-type configuration can make the molecular weight of the polyethylene relatively small. At the same time, compared with the E-type configuration nickel complex, the light-responsive Z-type configuration nickel complex provided by the present invention has unique advantages. There is a weak interaction between its ether chain and the bromine atom connected to the metal nickel. This characteristic makes the probability of poisoning and inactivation of the metal complex lower when copolymerizing with polar monomers. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0047] Figure 1 This is a single crystal structure diagram of E-(I)-3 provided in Example 6 of the present invention.

[0048] Figure 2 A single crystal structure diagram of E-(I)-5 is provided for Example 10 of the present invention.

[0049] Figure 3 This is a single crystal structure diagram of Z-(I)-5 provided in Example 20 of the present invention.

[0050] Figure 4 UV / visible spectra of E-(I)-1 to 5 and Z-(I)-5 provided in Examples 2, 4, 6, 8, 10 and 20 of the present invention, a) E-(I)-1; b) E-(I)-2; c) E-(I)-3; d) E-(I)-4; e) E-(I)-5; f) Z-(I)-5.

[0051] Figure 5 This is the elastic recovery diagram of polyethylene prepared by E-(I)-1 provided in Application Example 2 of the present invention.

[0052] Figure 6 This is the elastic recovery diagram of polyethylene prepared by E-(I)-1 provided in Application Example 3 of the present invention.

[0053] Figure 7 This is the elastic recovery diagram of polyethylene prepared by E-(I)-2 provided in Application Example 5 of the present invention.

[0054] Figure 8 This is the elastic recovery diagram of polyethylene prepared by E-(I)-2 provided in Application Example 6 of the present invention.

[0055] Fig. 9 This is the elastic recovery diagram of polyethylene prepared by E-(I)-3 provided in Application Example 8 of the present invention.

[0056] Fig.10 This is the elastic recovery diagram of polyethylene prepared by E-(I)-3 provided in Application Example 9 of the present invention.

[0057] Fig.11 The tensile stress-strain diagrams of polyethylene prepared by E-(I)-1 to 3 provided in Application Examples 1 to 9 of the present invention.

[0058] Fig.12 UV / visible spectra of E-(II)-1 (left) and E-(II)-2 (right) provided for Examples 22 and 26 of the present invention. DETAILED DESCRIPTION

[0059] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0060] In the present invention, the term "DME" represents ethylene glycol dimethyl ether; the term "terminal olefin-containing compound" refers to a small molecule organic compound with a C=C double bond at the end, including olefins, fatty acids containing terminal olefins, esters, etc. In α-diimine nickel / palladium complexes and pyridine imine nickel / palladium complexes, the "—" connected to Ni refers to a covalent bond or a coordination bond.

[0061] Unless otherwise specified, the processes of homopolymerization and copolymerization are well known to those skilled in the art and will not be described in detail here.

[0062] The following examples of the present invention show different aspects of the present invention. The data given include the synthesis of the ligand, the synthesis of the metal complex, the polymerization operation, the polymerization conditions and the polymerization product. All operations including reactions, preparations and storage were carried out under a dry inert atmosphere using standard Schlenk operations. Molecular weight and molecular weight distribution were determined by GPC. The determination was carried out on an Agilent PL-200 instrument using trichlorobenzene as solvent and Agilent PLgel Olexis as chromatographic column. Polystyrene was used as the standard and polyethylene was calibrated by universal calibration using Mark-Houwink parameters: K = 1.75 × 10 - 2 cm 3 ·g -1 , R = 0.67 (polystyrene), K = 5.90 × 10 -2 cm 3 ·g -1 , R=0.69 (polyethylene).

[0063] In the present invention, the preparation route of imine compounds is as follows:

[0064] Unless otherwise specified, compounds E-4 / Z-4 and E-8 / Z-8 used in the following examples were prepared by the following method: Under a nitrogen atmosphere, E-1 / Z-1 (1 mmol), commercial compound 5 (2 mmol) and tetrakis(triphenylphosphine)palladium (0.2 mmol) were added to a 200 mL Schlenk bottle, followed by 40 mL of toluene, 4 mL of ethanol and 8 mL of saturated aqueous sodium carbonate solution. The reaction bottle was sealed and placed in a 100°C metal bath for reaction for 24 h. After the reaction was completed and returned to room temperature, the reaction system was extracted with dichloromethane and water, and the organic phase was concentrated to obtain a crude product. The crude product was purified by column chromatography (petroleum ether / dichloromethane = 1 / 1) to obtain an off-white solid E-2 / Z-2; then, under a nitrogen atmosphere, E-2 / Z-2 (1mmol), compound 6 (CAS No.: 2750241-88-2) (1.5mmol) and tetrakis(triphenylphosphine)palladium (0.2mmol) were added to a 200mL Schlenk bottle, followed by 40mL toluene, 4mL ethanol and 8mL saturated sodium carbonate aqueous solution. The reaction bottle was sealed and placed in a 100°C metal bath for reaction for 24h. After the reaction was completed and returned to room temperature, the reaction system was extracted with dichloromethane and water, and the organic phase was concentrated to obtain a crude product. The crude product was purified by column chromatography (petroleum ether / dichloromethane = 1 / 1) to obtain an off-white solid E-3 / Z-3; wherein, R of compound 5 1The substituents are H, CN, OCH2CH2OCH3 or monosubstituted phenyl. Formula E-3 / Z-3 (0.75mmol), compound 7 (0.94mmol), and ZnCl2 (0.94mmol) were added to a 25mL Shrek bottle, replaced with nitrogen 3 times, and glacial acetic acid (10mL) was added. The reaction was stirred at 125°C for 10 hours under nitrogen protection. After the reaction was completed by monitoring by TLC, the reaction was terminated, cooled to room temperature, and a yellow precipitate precipitated from the reaction system. The yellow precipitate was filtered and washed three times with glacial acetic acid and ether. The above-obtained solid was dissolved in 50mL of dichloromethane, saturated potassium oxalate aqueous solution (10mL) was added and stirred for 12h, the organic layer was extracted with dichloromethane (50mL×3), dried with anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation to obtain a crude product. Subsequently, it was recrystallized from n-hexane solution to obtain the corresponding pure compound E-4 / Z-4, and the R of compound 7 2 The substituent is CH3, OCH3 or F.

[0065] The specific synthesis method of the metal nickel / palladium complex in the following examples:

[0066] In a glove box under argon atmosphere, add the prepared pure imine ligand compound E-4 / Z-4 (1.00 mmol), (DME)NiBr2 / (COD)PdMeCl (1.00 mmol), and 10 mL of anhydrous dichloromethane to a 50 mL round-bottom flask and stir at room temperature for 24 h. After the reaction is completed, remove the solvent in vacuo, and then filter the reaction system with n-hexane solution. The solid is recrystallized in dichloromethane and n-hexane solution to obtain a solid as the complex.

[0067] The reaction route is as follows:

[0068]

[0069] Example 1

[0070]

[0071] Specific synthesis of nickel complex E-(I)-1 ligand E-4-1: R of formula E-4 in the above reaction route 1 Substituents are H, R 2 When the substituent is CH3, the nickel complex E-(I)-1 ligand E-4-1 is obtained, and the yield of compound E-4-1 is 69%; yellow solid. Characterization data of the yellow solid: 1H NMR (600MHz, CDCl3): δ7.84-7.83(m,2H),7.85-7.64(m,2H),7.48-7.44(m,4H),7.41-7. 35(m,5H),7.28-7.25(m,8H),7.21-7.18(m,4H),7.11-7.10(m,4H),7.06-7.04(m,4H),6 .66(s,2H),5.26(s,2H),3.33-3.30(m,4H),3.20-3.17(m,4H),2.67(hept,J=6.9Hz,2H) ,2.18(s,3H),1.91(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.91(s,3H)ppm. 13 C{1H}NMR (151MHz, CDCl3): δ169.9,168.0,146.3,145.7,145.6,145.4,143.9,143.71,143.68,142 .5,142.0,140.7,139.8,137.3,135.9,135.4,135.3,131.7,131.4,129.7,129.4,128.78,128.76, 128.4,128.1,127.3,127.1,126.34,126.31,126.25,126.1,125.2,125.1,123.4,123.2,122.1,52 .3,32.4,32.1,30.9,30.8,28.3,23.4,23.2,21.3,16.9,16.0ppm.HRMS(ESI-TOF)m / z:[M+H]+calcd for C 73 H 69 N2 + ,973.5456;found,973.5471.

[0072] Example 2

[0073] Specific synthesis method of nickel complex E-(I)-1:

[0074]

[0075] In a glove box with argon atmosphere, α-diimine compound E-4-1 (1.00 mmol), (DME)NiBr2 (1.00 mmol), and 10 mL of anhydrous dichloromethane prepared in Example 1 were added to a 50 mL round-bottom flask and stirred at room temperature for 24 h. After the reaction was completed, the solvent was removed in vacuo, and then the reaction system was filtered using a n-hexane solution. The solid was recrystallized from a dichloromethane and n-hexane solution to obtain a solid, namely, the metal nickel complex E-(I)-1, with a yield of 74%. ESI-MS (m / z): [M-Br] + Calculate for C 73 H 68 BrN2Ni + ,1109.3914; found,1109.3934.

[0076] Example 3

[0077]

[0078] Specific synthesis of nickel complex E-(I)-2 ligand E-4-2: R of formula E-4 1 Substituents are H, R 2 When the substituent is OCH3, the yield of compound E-4-2 is 67%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ7.84-7.83(m,2H),7.85-7.64(m,2H),7.48-7.44(m,4H),7.41-7. 35(m,5H),7.28-7.26(m,8H),7.21-7.17(m,4H),7.12-7.11(m,4H),7.07-7.05(m,4H),6 .44(s,2H),5.27(s,2H),3.56(s,3H),3.32-3.30(m,4H),3.20-3.17(m,4H),2.66(hept, J=7.0Hz,2H),1.90(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.94(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3): δ170.5,168.1,155.2,146.4,145.8,145.4,144.0,143.7,143.3,142 .3,142.0,141.7,140.7,139.8,137.4,135.9,135.5,135.3,132.9,129.7,129.4,128.8,128 .5,128.2,127.3,127.1,126.5,126.3,126.3,125.2,125.1,123.4,123.2,122.2,114.0,55. 2,52.5,32.5,32.2,30.94,30.87,28.4,23.5,23.2,16.9,16.1ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 73 H 69 N2O + ,989.5405;found,989.5417.

[0079] Example 4

[0080] Synthesis of Nickel Complex E-(I)-2:

[0081]

[0082] The preparation method is the same as that of Example 2, and the α-diimine compound E-4-2 prepared in Example 3 is added to obtain E-(I)-2 with a yield of 75%. ESI-MS (m / z): [M-Br] + Calculate for C 73 H 68 BrN2NiO + ,1125.3863; found,1125.3850.

[0083] Example 5

[0084]

[0085] Specific synthesis of nickel complex E-(I)-3 ligand E-4-3: R of formula E-4 1 Substituents are H, R 2 When the substituent is F, the yield of compound E-4-3 is 67%; yellow solid. Characterization data of the yellow solid: 1H NMR (600MHz, CDCl3): δ7.84(s,1H),7.82(s,1H),7.65-7.64(m,2H),7.48-7.44(m,4H),7 .44-7.35(m,5H),7.29-7.26(m,8H),7.23-7.19(m,4H),7.10-7.09(m,4H),7.05-7.04(m ,4H),6.60-6.58(m,2H),5.26(s,2H),3.33-3.29(m,4H),3.20-3.17(m,4H),2.65(hept, J=6.9Hz,2H),1.90(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.92(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ170.7,167.9,159.0(d, 1 J CF =240.2Hz),146.4,145.8,145.3,143.94,143.92,143.8,142.8,142.0,141.8,140.6,139.9,137.5,135.9,135.5,135.3,133.6(d, 3 J CF =6.6Hz),129.6,129.4,128.8,128.6,128.3,127.3,127.1,126.7,126.5,126.33,126.30,125.2,125.1,123.4,123.2,122.2,115.1(d, 2 J CF =23.3Hz),52.4,32.5,32.2,30.93,30.87,28.4,23.5,23.2,16.9,16.1ppm. 19 F{ 1 H}NMR(565MHz,CDCl3):δ-120.24ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 72 H 66 FN2 + ,977.5205;found,977.5218.

[0086] Example 6

[0087] Synthesis of Nickel Complex E-(I)-3:

[0088]

[0089] The preparation method is the same as that of Example 2, and the α-diimine compound E-4-3 prepared in Example 5 is added to obtain E-(I)-3 with a yield of 75%. ESI-MS (m / z): [M-Br] + Calculate for C 73 H 65 BrFN2Ni + ,1113.3663; found,1113.3648.

[0090] Example 7

[0091]

[0092] Specific synthesis of nickel complex E-(I)-4 ligand E-4-4: R of formula E-4 1 The substituents are CN, R 2 When the substituent is CH3, the yield of compound E-4-4 is 55%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3) δ7.82 (d, J = 4.8Hz, 2H), 7.76-7.73 (m, 4H), 7.47-7.40 (m, 1H), 7.47-7.40 ( m,4H),7.37(s,2H),7.28-7.26(m,6H),7.20-7.18(m,4H),7.11(d,J=7.1Hz,4H),7.05(d,J=7. 7Hz,4H),6.66(s,2H),5.26(s,2H),3.34-3.28(m,4H),3.22-3.18(m,4H),2.67(hept,J=6.9Hz ,2H),2.18(s,3H),1.91(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.91(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3) δ169.8,168.1,147.9,146.5,145.8,145.6,145.5,144.4,143.7,143.5 ,142.6,140.8,137.8,137.3,136.6,135.4,134.9,132.6,131.8,131.4,129.8,129.5,128.8,1 28.5,128.1,127.8,126.6,126.4,126.1,125.6,125.2,123.30,123.28,122.1,119.1,110.7, 52.3,32.5,32.1,31.0,30.8,28.4,23.5,23.2,21.3,16.9,16.1ppm.HRMS(ESI-TOF)m / z:[M+K] + Calculate for C 74 H 67 N3K + ,1036.4967;found,1036.4978.

[0093] Example 8

[0094] Synthesis of Nickel Complex E-(I)-4:

[0095]

[0096] The preparation method is the same as that of Example 2, and the α-diimine compound E-4-4 prepared in Example 7 is added to obtain E-(I)-4 with a yield of 60%. ESI-MS (m / z): [M-Br] + Calculate for C 74 H 67 BrN3Ni + ,1134.3866; found,1134.4000.

[0097] Example 9

[0098]

[0099] Specific synthesis of nickel complex E-(I)-5 ligand E-4-5: R of formula E-4 1 The substituent is OCH2CH2OCH3, R 2 When the substituent is CH3, the yield of compound E-4-5 is 51%; yellow solid. Characterization data of the yellow solid: 1H NMR (600MHz, CDCl3) δ7.82-7.80(m,2H),7.57-7.56(m,2H),7.45-7.44(m,1H),7.40-7.36(m,5H),7.2 8-7.24(m,8H),7.20-7.18(m,4H),7.11(d,J=7.1Hz,4H),7.05-7.03(m,6H),6.66(s,2H),5.26(s,2H), 4.19-4.18(m,2H),3.80-3.78(m,2H),3.48(s,3H),3.32-3.30(m,4H),3.18-3.15(m,4H),2.67(hept, J=6.9Hz,2H),2.17(s,3H),1.91(s,3H),1.28(d,J=6.9Hz,6H),1.22(d,J=6.8Hz,6H),0.91(s,3H)ppm. 13 C{ 1 H}NMR(151MHz,CDCl3)δ169.9,168.0,158.3,145.80,145.76,145.7,145.4,143.9,143.8,143.7,1 42.6,140.7,139.4,137.4,135.8,135.6,135.3,134.8,131.8,131.5,129.8,129.5,128.8,128.5,1 28.3,128.1,126.4,126.3,126.1,125.9,125.2,125.1,123.2,123.0,122.2,115.0,71.1,67.5,59. 3,52.3,32.5,32.2,30.89,30.87,28.4,23.5,23.2,21.3,16.9,16.1ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 76 H 75 N2O2 + ,1047.5824;found,1047.5837.

[0100] Example 10

[0101] Synthesis of Nickel Complex E-(I)-5:

[0102]

[0103] The preparation method is the same as that of Example 2, and the α-diimine compound E-4-5 prepared in Example 9 is added to obtain E-(I)-5 with a yield of 90%. ESI-MS (m / z): [M-Br] + Calculate for C 76 H 74 BrN2NiO2 + ,1183.4282; found,1183.4289.

[0104] Embodiment 11

[0105]

[0106] Specific synthesis of nickel complex Z-(I)-1 ligand Z-3-1: R of formula Z-4 1 Substituents are H, R 2 When the substituent is CH3, the yield of compound Z-4-1 is 52%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28 -7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6 .66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept,J=6.9Hz,2 H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141.2 ,141.1,139.7,138.4,137.0,135.3,135.2,135.1,133.8,131.7,131.4,129.8,129.4,128.8,12 8.4,128.1,128.0,126.4,126.3,126.1,126.0,125.4,125.3,122.1,122.0,121.3,114.8,52.3, 35.1,34.9,30.4,30.3,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H]+calcd for C 73 H 69 N2 + ,973.5456;found,973.5462.

[0107] Example 12

[0108] Synthesis of Nickel Complex Z-(I)-1:

[0109]

[0110] The preparation method is the same as that of Example 2, and the α-diimine compound Z-4-1 prepared in Example 11 is added to obtain Z-(I)-1 with a yield of 68%. ESI-MS (m / z): [M-Br] + Calculate for C 73 H 68 BrN2Ni + ,1109.3914; found,1109.3943.

[0111] Example 13

[0112]

[0113] Specific synthesis of nickel complex Z-(I)-2 ligand Z-4-2: R of formula Z-4 1 Substituents are H, R 2 When the substituent is OCH3, the yield of compound Z-4-2 is 53%; yellow solid. Characterization data of the yellow solid: 1H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28 -7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6 .66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept,J=6.9Hz,2 H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141. 2,141.1,139.7,138.4,137.0,135.3,135.2,135.1,133.8,131.7,131.4,129.8,129.4,128.8 ,128.4,128.1,128.0,126.4,126.3,126.1,126.0,125.4,125.3,122.1,122.0,121.3,114.8, 52.3,35.1,34.9,30.4,30.3,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 73 H 69 N2O + ,989.5405;found,989.5412.

[0114] Embodiment 14

[0115] Synthesis of Nickel Complex Z-(I)-2:

[0116]

[0117] The preparation method is the same as that of Example 2, and the α-diimine compound Z-4-2 prepared in Example 13 is added to obtain Z-(I)-2 with a yield of 77%. ESI-MS (m / z): [M-Br] + Calculate for C 73 H68 BrN2NiO + ,1125.3863; found,1125.3868.

[0118] Embodiment 15

[0119]

[0120] Specific synthesis of nickel complex Z-(I)-3 ligand Z-4-3: R of formula Z-4 1 The substituent is H, and R 2 When the substituent is F, the yield of compound Z-4-3 is 52%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7 .28-7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m ,4H),6.66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept, J=6.9Hz,2H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141. 2,141.1,139.7,138.4,137.0,135.3,135.2,135.1,133.8,131.7,131.4,129.8,129.4,128.8 ,128.4,128.1,128.0,126.4,126.3,126.1,126.0,125.4,125.3,122.1,122.0,121.3,114.8, 52.3,35.1,34.9,30.4,30.3,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 72 H 66 FN2 +,977.5205;found,977.5214.

[0121] Example 16

[0122] Synthesis of Nickel Complex Z-(I)-3:

[0123]

[0124] The preparation method is the same as that of Example 2, and the α-diimine compound Z-4-3 prepared in Example 15 is added to obtain Z-(I)-3 with a yield of 75%. ESI-MS (m / z): [M-Br] + Calculate for C 73 H 65 BrFN2Ni + ,1113.3663;found,1113.3677.

[0125] Embodiment 17

[0126]

[0127] Specific synthesis of nickel complex Z-(I)-4 ligand Z-4-4: R of formula Z-4 1 The substituents are CN, R 2 When the substituent is CH3, the yield of compound Z-4-4 is 54%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28 -7.27(m,4H),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6 .66-6.64(m,4H),5.23(s,2H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hept,J=6.9Hz,2 H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141.2 ,141.1,139.7,138.4,137.0,135.3,135.24,135.21,133.8,131.7,131.4,129.8,129.4,128.8, 128.4,128.1,128.0,126.4,126.3,126.1,126.0,125.41,125.37,122.1,122.0,121.3,114.8,5 2.3,35.1,34.9,30.42,30.35,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+K] + Calculate for C 74 H 67 N3K + ,1036.4967;found,1036.4972.

[0128] Embodiment 18

[0129] Synthesis of Nickel Complex Z-(I)-4:

[0130]

[0131] The preparation method is the same as that of Example 2, and the α-diimine compound Z-4-4 prepared in Example 17 is added to obtain Z-(I)-4 with a yield of 60%. ESI-MS (m / z): [M-Br] + Calculate for C 74 H 67 BrN3Ni + ,1134.3866;found,1134.3878.

[0132] Embodiment 19

[0133]

[0134] Specific synthesis of nickel complex Z-(I)-5 ligand: R of formula Z-4 1 The substituent is OCH2CH2OCH3, R 2 When the substituent is CH3, the yield of compound Z-4-5 is 55%; yellow solid. Characterization data of the yellow solid: 1H NMR (600MHz, CDCl3): δ8.47(s,1H),8.39(s,1H),7.44-7.43(m,1H),7.38-7.32(m,3H),7.28-7.27(m,4H ),7.25-7.23(m,8H),7.20-7.16(m,4H),7.09-7.08(m,4H),7.04-7.02(m,4H),6.66-6.64(m,4H),5.23(s ,2H),3.96-3.94(m,2H),3.59-3.58(m,2H),3.32(s,3H),3.06-3.03(m,4H),2.90-2.88(m,4H),2.56(hep t,J=6.9Hz,2H),2.17(s,3H),1.86(s,3H),1.11(d,J=6.9Hz,6H),1.03(d,J=6.8Hz,6H),0.87(s,3H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ169.8,168.0,158.1,146.9,146.8,145.6,145.3,143.7,142.5,141.2,141 .1,139.7,138.4,137.0,135.3,135.24,135.21,133.8,131.7,131.4,129.8,129.4,128.8,128.4,12 8.1,128.0,126.4,126.3,126.1,126.0,125.41,125.37,122.1,122.0,121.3,114.8,71.0,67.2,59 .1,52.3,35.1,34.9,30.42,30.35,28.3,23.4,23.0,21.3,16.8,16.0ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 76 H 75 N2O2 + ,1047.5824;found,1047.5831.

[0135] Embodiment 20

[0136] Synthesis of Nickel Complex Z-(I)-5:

[0137]

[0138] The preparation method is the same as that of Example 2, and the α-diimine compound Z-4-5 prepared in Example 19 is added to obtain Z-(I)-5 with a yield of 90%. ESI-MS (m / z): [M-Br] + Calculate for C 76 H 74 BrN2NiO2 + ,1183.4282;found,1183.4275.

[0139] As attached Figure 2 and Figure 3 As shown in Figure 2, a lot of valuable data information was found in the two single crystals E-(I)-5 and Z-(I)-5. Specifically, the distance between Br2 and H11 in the E-(I)-5 single crystal is In Z-(I)-5 single crystal, It is worth noting that both distances are smaller than the sum of the van der Waals radii of Br and H. At the same time, the distance between Br1 and H24 showed an obvious trend of change, as shown by the Shortened to Z-(I)-5 In addition, from the perspective of bond angle, in the E-(I)-5 single crystal, the angle formed by Br2-Ni1-Br1 is 118.20°, while in the Z-(I)-5 single crystal, the corresponding Br2-Ni1-Br1 angle increases to 123.21°. In addition, the distance between H(H73) and Br(Br1) is The above-mentioned key distances, angles and other data strongly indicate the existence of weak hydrogen bond interactions between CH···Br-M. These data provide a solid basis and strong support for the existence of weak hydrogen bond interactions in this system.

[0140] The present invention provides a specific synthesis method of pyridine imine compound E / Z-8:

[0141] The preparation method of α-bis-imine compound E-4 / Z-4 is consistent with that of compound 9, and compound 7 is replaced by compound 9, and the corresponding pure compound E-8 / Z-8 is obtained by recrystallization from n-hexane solution. The preparation method of metal complex E-(II) / Z-(II) is also consistent with that of bis-imine complex. The reaction route is shown below:

[0142]

[0143] Embodiment 21

[0144]

[0145] Specific synthesis of nickel complex E-(II)-1 ligand E-8-1: R of formula E-8 1 When the substituent is H, the yield of compound E-8-1 is 83%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ8.69(s,1H),8.39(d,J=8.1Hz,1H),7.85(d,J=9.7Hz,2H),7.83-7.80(m,1H),7.64-7.63(m,2H ),7.48-7.34(m,10H),3.34-3.29(m,4H),3.19-3.16(m,4H),2.86-2.79(m,2H),2.29(s,3H),1.24-1.22(m,12H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.2,156.5,148.6,146.4,145.8,145.7,144.0,1 43.7,142.0,140.8,139.8,137.2,136.5,136.2,136.0,135.4,128.8,127.3 ,127.1,126.4,126.3,125.2,125.1,124.8,123.4,123.3,122.2,121.4,32. 5,32.2,30.94,30.88,28.5,23.4,23.0,17.6ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 43 H 43 N2 + ,587.3421;found,587.3417.

[0146] Embodiment 22

[0147] Synthesis of Nickel Complex E-(II)-1:

[0148]

[0149] The method is the same as that of Example 2, and the pyridine imine compound E-8-1 prepared in Example 21 is added to obtain E-(II)-1 with a yield of 90%. ESI-MS (m / z): [M-Br] + Calculate for, C 43 H 42 BrN2Ni + ,723.1879;found,723.1889.

[0150] Embodiment 23

[0151]

[0152] Specific synthesis of nickel complex Z-(II)-1 ligand Z-8-1: R of formula Z-8 1 When the substituent is H, the yield of compound Z-8-1 is 71%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ8.67(d,J=4.2Hz,1H),8.50(s,1H),8.44(s,1H),8 .37-8.35(m,1H),7.82-7.79(m,1H),7.47-7.46(m,1H),7.41-7.39(m,2H) ,7.37-7.34(m,4H),7.31(s,2H),7.16-7.10(m,3H),3.07-3.03(m,4H),2 .91-2.88(m,4H),2.73-2.67(m,2H),2.22(s,3H),1.06-1.04(m,12H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.0,156.5,148.6,147.4,146.8,145.7,141.3, 141.1,139.8,138.9,136.7,136.5,136.2,135.4,135.0,128.6,127.0,126 .8,126.5,126.3,125.41,125.39,124.8,122.0,122.0,121.9,121.4,35.1 ,34.9,30.44,30.41,28.5,23.3,22.7,17.5ppm.HRMS(ESI-TOF)m / z:[M+H] + Calculate for C 43 H 43 N2 + ,587.3421;found,587.3437.

[0153] Embodiment 24

[0154] Synthesis of Nickel Complex Z-(II)-1:

[0155]

[0156] The method is the same as that of Example 2, and the pyridine imine compound Z-8-1 prepared in Example 23 is added to obtain Z-(II)-1 with a yield of 90%. ESI-MS (m / z): [M-Br] +Calculate for, C 43 H 42 BrN2Ni + ,723.1879;found,723.1883.

[0157] Embodiment 25

[0158]

[0159] Specific synthesis of nickel complex E-(II)-2 and palladium complex E-(II)-3 ligand E-8-2: R of formula E-8 1 When the substituent is Ph, the yield of compound E-8-2 is 87%; yellow solid. Characterization data of the yellow solid: 1 H NMR (600MHz, CDCl3): δ8.69(d,J=4.8Hz,1H),8.39(d,J=7.9Hz,1H),7.89(s,1H),7.86(s,1H),7.84-7.81(m,1H),7.73-7.69(m,4H),7.66-7.65(m ,2H),7.49-7.45(m,4H),7.41-7.35(m,6H),3.34-3.33(m,4H),3.20-3.1 8(m,4H),2.82(hept,J=6.8Hz,2H),2.29(s,3H),1.24-1.22(m,12H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.2,156.5,148.6,146.5,145.8,145.7,144.0,143.7 ,140.9,140.84,140.82,140.0,139.3,137.2,136.5,136.2,136.0,135.4,128.8, 127.6,127.5,127.3,127.1,126.4,126.1,125.3,125.1,124.8,123.3,122.2,12 1.4,32.5,32.2,31.0,30.9,28.5,23.3,23.0,17.5ppm.HRMS(ESI-TOF)m / z:[M+H] + calcdfor C 49 H 47 N2 + ,663.3734;found,663.3741.

[0160] Embodiment 26

[0161] Synthesis of Nickel Complex E-(II)-2:

[0162]

[0163] The method is the same as that of Example 2, and the pyridine imine compound E-8-2 prepared in Example 25 is added to obtain E-(II)-2 with a yield of 90%. ESI-MS (m / z): [M-Br] + Calculate for, C 49 H 46 BrN2Ni + ,799.2192;found,799.2195.

[0164] Embodiment 27

[0165] Synthesis of palladium complex E-(II)-3:

[0166]

[0167] In a glove box with an argon atmosphere, the pyridine imine compound E-8-2 (1.00 mmol), (COD)PdMeCl (1.00 mmol), and 10 mL of anhydrous dichloromethane prepared in Example 25 were added to a 50 mL round-bottom flask and stirred at room temperature for 24 h. After the reaction was completed, the solvent was removed in vacuo, and then the reaction system was filtered using a n-hexane solution. The solid was recrystallized from a dichloromethane and n-hexane solution to obtain a solid, namely, complex E-(II)-3, with a yield of 89%. ESI-MS (m / z): [M-Br] + Calculate for C 49 H 46 BrN2Ni + ,783.2925;found,783.2935.

[0168] Embodiment 28

[0169]

[0170] Specific synthesis of nickel complex Z-(II)-2 and palladium complex Z-(II)-3 ligand Z-8-2: R of formula Z-8 1 When the substituent is Ph, the yield of the compound is 70%; yellow solid. Characterization data of the yellow solid: 1H NMR (600MHz, CDCl3): δ8.66-8.65(m,1H),8.54(s,1H),8.51(s,1H),8.32-8.31m,1H) ,7.77-7.74(m,1H),7.60-7.58(m,2H),7.48-7.47(m,1H),7.45-7.44(m,3H),7.39-7 .34(m,7H),7.33(s,2H),7.30-7.28(m,1H),3.07-3.04(m,4H),2.92-2.89(m,4H),2. 70(hept,J=6.9Hz,2H),2.19(s,3H),1.05(d,J=6.9Hz,6H),0.98(d,J=6.9Hz,6H)ppm. 13 C{ 1 H}NMR (151MHz, CDCl3): δ167.0,156.5,148.6,147.5,146.8,145.7,141.3,141.1,14 0.7,140.0,139.9,139.5,138.3,136.8,136.4,136.2,135.5,135.0,128.6,127.4,12 7.3,127.1,126.9,126.5,126.2,125.5,125.4,124.7,122.3,122.1,121.7,121.4,3 5.1,34.9,30.44,30.43,28.5,23.2,22.8,17.4ppm.HRMS(ESI-TOF)m / z:[M+H]+calcd for C 49 H 47 N2 + ,663.3734;found,663.3744.

[0171] Embodiment 29

[0172] Synthesis of Nickel Complex Z-(II)-2:

[0173]

[0174] The method is the same as Example 2, and the pyridine imine compound Z-8-2 prepared in Example 28 is added to obtain Z-(II)-2, 90%. ESI-MS (m / z): [M-Br] + Calculate for C 49 H 46 BrN2Ni + ,799.2192;found,799.2199.

[0175] Embodiment 30

[0176] Synthesis of Nickel Complex Z-(II)-3:

[0177]

[0178] The method is the same as Example 27, and the pyridine imine compound Z-8-2 prepared in Example 28 is added to obtain Z-(II)-3 with a yield of 88%. ESI-MS (m / z): [M-Br] + Calculate for C 49 H 46 BrN2Ni + ,783.2925;found,783.2933.

[0179] Application Examples 1 to 9 show that at different temperatures, the imine nickel complexes E-(I)-1 to 3 with different substituents exhibit different catalytic characteristics in the ethylene homopolymerization process: under 0.8 MPa ethylene pressure, dark conditions, and different temperatures, this type of catalyst has high catalytic activity and ultra-high molecular weight in ethylene polymerization, which also shows that the catalyst has high temperature resistance.

[0180] Application Example 1

[0181] Under the anhydrous and oxygen-free conditions in the glove box, add anhydrous toluene (48 mL) to a 100 mL thick-walled quartz dish and place it in the intelligent olefin polymerization device; evacuate the reactor, pass ethylene to saturation, and add AlEt2Cl (0.5 mL, 1M intoluene); preheat and stir at 30 ° C, add a dichloromethane (2 mL) solution of α-diimine nickel complex E-(I)-1 (1 μmol) and adjust the ethylene pressure to 0.8 MPa, and stir for 10 minutes. After the reaction, the reactants were quenched with 5% hydrochloric acid in ethanol. After precipitation, filtration, and washing, the polymer was vacuum dried at 50 ° C to constant weight to obtain a polymerization product. The specific experimental results are shown in Table 1.

[0182] Application Example 2

[0183] The experimental process is the same as that of Application Example 1, except that the reaction temperature is changed from 30°C to 50°C. The results are shown in Table 1.

[0184] Application Example 3

[0185] The experimental process is the same as that of Application Example 1, except that the reaction temperature is changed from 30°C to 80°C. The results are shown in Table 1.

[0186] Table 1

[0187]

[0188] Application Examples 1 to 3 show the catalytic performance of E-(I)-1 catalyst at different temperatures at a pressure of 0.8 MPa and a reaction time of 10 min. It is still active at 80°C, reflecting the high temperature resistance of the catalyst. The molecular weight of E-(I)-1 catalyst decreases with increasing temperature. This is because the chain transfer rate increases with increasing temperature, resulting in a decrease in molecular weight and an increase in branching degree.

[0189] Application Example 4

[0190] The experimental process is the same as that of Application Example 1, except that the catalyst is changed from E-(I)-1 to E-(I)-2, see Table 2.

[0191] Application Example 5

[0192] The experimental process is the same as that of Application Example 4, except that the reaction temperature is changed from 30°C to 50°C, see Table 2.

[0193] Application Example 6

[0194] The experimental process is the same as that of Application Example 4, except that the reaction temperature is changed from 30°C to 80°C, see Table 2.

[0195] Table 2

[0196]

[0197]

[0198] Application Examples 4 to 6 show the catalytic performance of E-(I)-2 catalyst at different temperatures under a pressure of 0.8 MPa and a reaction time of 10 min. It is still active at 80°C, reflecting the high temperature resistance of the catalyst. Compared with E-(I)-1 catalyst, the substituent of E-(I)-2 catalyst is methoxy, and the molecular weight is slightly increased. As the temperature of E-(I)-2 catalyst increases, the molecular weight shows a decreasing trend.

[0199] Application Example 7

[0200] The experimental process is the same as that of Application Example 1, except that the catalyst is changed from E-(I)-1 to E-(I)-3, see Table 3.

[0201] Application Example 8

[0202] The experimental process is the same as that of Application Example 7, except that the reaction temperature is changed from 30°C to 50°C, see Table 3.

[0203] Application Example 9

[0204] The experimental process is the same as that of Application Example 7, except that the reaction temperature is changed from 30°C to 80°C, see Table 3.

[0205] Table 3

[0206]

[0207] Application Examples 7 to 9 demonstrate the catalytic performance of E-(I)-3 catalyst at different temperatures under a pressure of 0.8 MPa and a reaction time of 10 min. Compared with E-(I)-1, the substituent of E-(I)-3 catalyst is F, and F interacts with the β-H on the polymer, resulting in a slight increase in the molecular weight. As the temperature increases, the molecular weight of E-(I)-3 catalyst shows a decreasing trend. This is because the electron-withdrawing F group is easily affected by temperature, resulting in an increase in the chain transfer rate, a decrease in the molecular weight, and an increase in the degree of branching. In addition, the elastic recovery rate of the polymer obtained by catalyzing the homopolymerization of ethylene by catalyst E-(I)-3 at 50°C is as high as 92%. As shown in the attached figure, Fig. 9 shown.

[0208] Application Examples 10 to 27 show that nickel imine complexes with different substituents exhibit different catalytic characteristics in ethylene homopolymerization under different lighting environments: compared with the dark condition, the E-type catalyst after illumination has higher catalytic activity, higher molecular weight and lower degree of branching in ethylene polymerization.

[0209] By detecting the changes in the UV-visible absorption spectrum in dichloromethane solution, the photoisomerization behavior of nickel catalysts was further investigated (see Appendix). Figure 4 ). Under the irradiation condition of ultraviolet light with a wavelength set to 365nm, the absorbance of E-(I)-1, E-(I)-2 and E-(I)-3 in the wavelength range of 252nm to 359nm showed a gradual decrease. Among them, E-(I)-5 with an oxygen atom with a lone pair of electrons or E-(I)-4 containing a cyano group can form a conjugated system with the π bond of the benzene ring. This conjugation effect greatly promotes the occurrence of p-π conjugation. This interaction essentially broadens the range of electron activity and significantly improves the excitation efficiency, which in turn causes the π→π* transition absorption band to red-shift toward a longer wavelength.

[0210] As for E-(I)-4, its absorbance showed a gradually decreasing trend in the wavelength range of 262nm to 362nm; similarly, the absorbance of E-(I)-5 also showed a gradually decreasing trend in the wavelength range of 256nm to 361nm. However, in sharp contrast, when Z-(I)-5 was irradiated with visible light of a wavelength of 405nm, its absorbance showed a gradually increasing trend.

[0211] The characteristic absorption peak of rigid diphenylethylene is around 325nm to 365nm. E-(I)-5 has a double peak here. As the irradiation time of 365nm ultraviolet lamp increases, the absorption intensity weakens. However, Z-(I)-5 only has a peak here. As the irradiation time of 405nm ultraviolet lamp increases, a double peak appears and the ultraviolet absorption intensity increases.

[0212] It is worth mentioning that in the UV-visible absorption spectra of E-(I)-5 and Z-(I)-5, isosbestic points were observed at approximately 256nm and 361nm. This phenomenon strongly proves that the two configuration isomers have the ability to transform into each other under light conditions, providing a key experimental basis for in-depth research on their photochemical properties and related reaction mechanisms. In addition, the time required for the E-configuration catalyst to reach the photostable state is longer than that required for the Z-configuration catalyst to reach the photostable state, and the required ultraviolet irradiation wavelength is shorter, which verifies that the E-configuration has lower energy and more stable structure in thermodynamics.

[0213] Application Example 10

[0214] The operation was the same as that in Application Example 1, except that anhydrous toluene was replaced with anhydrous dichloromethane (30 mL), the ethylene pressure was adjusted to 0.2 MPa, the reaction time was adjusted to 30 min, and the reaction temperature was adjusted to 0°C. The specific experimental results are shown in Table 4.

[0215] Application Example 11

[0216] According to the attached Figure 4 The results of the ultraviolet-visible absorption spectrum show that the catalyst E-(I) is in a stable state after being irradiated with 365nm ultraviolet light for 420 seconds, and there is no conversion from the E-form configuration to the Z-form configuration, so the illumination time of the catalyst before polymerization is determined to be 10 minutes. The experimental process is the same as that of Application Example 10, except that the added catalyst E-(I)-1 needs to be added to the reaction system after 365nm ultraviolet irradiation for 10 minutes. The specific experimental results are shown in Table 4.

[0217] Table 4

[0218]

[0219] Application Examples 10-11 demonstrate the catalytic performance of E-(I)-1 catalyst at 0°C under a pressure of 0.2 MPa, a reaction time of 30 min. Compared with no illumination, E-(I)-1 catalyst exhibits higher activity after illumination, resulting in a decrease in chain transfer rate, an upward trend in molecular weight, and a decrease in branching degree.

[0220] Application Example 12

[0221] The experimental process is the same as that of Application Example 10, except that the catalyst is changed from E-(I)-1 to E-(I)-2, see Table 5.

[0222] Application Example 13

[0223] The experimental process is the same as that of Application Example 11, except that the catalyst is changed from E-(I)-1 to E-(I)-2, see Table 5.

[0224] Table 5

[0225]

[0226] Application Examples 12-13 demonstrate the catalytic performance of E-(I)-2 catalyst at 0°C under a pressure of 0.2 MPa, a reaction time of 30 min. Compared with no illumination, E-(I)-2 catalyst exhibits higher activity after illumination, resulting in a decrease in chain transfer rate, an upward trend in molecular weight, and a decrease in branching degree.

[0227] Application Example 14

[0228] The experimental process is the same as that of Application Example 10, except that the catalyst is changed from E-(I)-1 to E-(I)-3, see Table 6.

[0229] Application Example 15

[0230] The experimental process is the same as that of Application Example 11, except that the catalyst is changed from E-(I)-1 to E-(I)-3, see Table 6.

[0231] Table 6

[0232]

[0233] Application Examples 14-15 demonstrate the catalytic performance of E-(I)-3 catalyst at 0°C under a pressure of 0.2 MPa, a reaction time of 30 min. Compared with no illumination, E-(I)-3 catalyst exhibits higher activity after illumination, resulting in a decrease in chain transfer rate, an upward trend in molecular weight, and a decrease in branching degree.

[0234] Application Example 16

[0235] The experimental process is the same as that of Application Example 10, except that the catalyst is changed from E-(I)-1 to E-(I)-4, see Table 7.

[0236] Application Example 17

[0237] The experimental process is the same as that of Application Example 11, except that the catalyst is changed from E-(I)-1 to E-(I)-4, see Table 7.

[0238] Table 7

[0239]

[0240]

[0241] Application Examples 16-17 demonstrate the catalytic performance of E-(I)-4 catalyst at 0°C under a pressure of 0.2 MPa, a reaction time of 30 min. Compared with no illumination, E-(I)-4 catalyst exhibits higher activity after illumination, resulting in a decrease in chain transfer rate, an upward trend in molecular weight, and a decrease in branching degree.

[0242] Application Example 18

[0243] The experimental process is the same as that of Application Example 10, except that the catalyst is changed from E-(I)-1 to E-(I)-5, see Table 8.

[0244] Application Example 19

[0245] The experimental process is the same as that of Application Example 11, except that the catalyst is changed from E-(I)-1 to E-(I)-5, see Table 8.

[0246] Application Examples 18 to 19 demonstrate the catalytic performance of the E-(I)-5 catalyst at 0°C at a pressure of 0.2 MPa and a reaction time of 30 min. Compared with the case without illumination, the E-(I)-5 catalyst exhibits higher activity after illumination, due to the weak interaction between the hydrogen on the ether chain of the Z-type catalyst and the bromine atom on the nickel metal after illumination, resulting in a decrease in the chain transfer rate, an upward trend in the molecular weight, and a decrease in the degree of branching.

[0247] Table 8

[0248]

[0249] Application Example 20

[0250] The experimental process is the same as that of Application Example 18, except that the reaction temperature is changed from 0°C to room temperature, see Table 9.

[0251] Application Example 21

[0252] The experimental process is the same as that of Application Example 19, except that the reaction temperature is changed from 0°C to room temperature, see Table 9.

[0253] Table 9

[0254]

[0255] Application Examples 20-21 demonstrate the catalytic performance of E-(I)-5 catalyst at room temperature under a pressure of 0.2 MPa and a reaction time of 30 min. Compared with the case without illumination, E-(I)-5 catalyst exhibits similar activity and molecular weight after illumination; however, due to the conversion of part of the E-form to the Z-form configuration after illumination with 405 nm ultraviolet light, there is a weak interaction between the hydrogen on the ether chain of the Z-form catalyst and the bromine atom connected to the metal nickel, resulting in a decrease in the branching degree of the polymer.

[0256] Application Example 22

[0257] The operation was the same as that in Application Example 1, except that the amount of anhydrous toluene solvent was changed to 18.5 mL, the ethylene pressure was adjusted to 0.2 MPa, and the reaction was stirred for 60 min. See Table 10.

[0258] Application Example 23

[0259] According to the attached Fig.12 The results of the UV-visible absorption spectrum show that the catalyst E-(II)-1 or E-(II)-2 is stable after irradiation with 365nm UV light for 210 seconds, and there is no conversion from E-form configuration to Z-form configuration, so the illumination time of the catalyst before polymerization is determined to be 5 minutes. The experimental process is the same as that of Application Example 22, except that the added catalyst E-(II)-1 needs to be added to the reaction system after 365nm UV irradiation for 5 minutes. The specific experimental results are shown in Table 10.

[0260] Table 10

[0261]

[0262] Application Examples 22-23 demonstrate the catalytic performance of E-(II)-1 catalyst at room temperature under a pressure of 0.2 MPa and a reaction time of 60 min. Compared with the case without illumination, E-(II)-1 catalyst exhibits similar activity and molecular weight after illumination, and the difference is not obvious.

[0263] Application Example 24

[0264] The experimental process is the same as that of Application Example 22, except that the catalyst is changed from E-(II)-1 to E-(II)-2, see Table 11.

[0265] Application Example 25

[0266] The experimental process is the same as that of Application Example 23, except that the catalyst is changed from E-(II)-1 to E-(II)-2, see Table 11.

[0267] Table 11

[0268]

[0269] Application Examples 24-25 demonstrate the catalytic performance of E-(II)-2 catalyst at room temperature under a pressure of 0.2 MPa and a reaction time of 60 min. Compared with the case without illumination, E-(II)-1 catalyst exhibits relatively higher activity and molecular weight after illumination, which may be due to the interaction between the benzene ring on the ligand and nickel, resulting in a decrease in the transfer rate, an increase in the molecular weight, and a decrease in the degree of branching.

[0270] Application Example 26

[0271] Under the anhydrous and oxygen-free conditions in the glove box, NaBArF (2 eq.) and anhydrous dichloromethane (38 mL) were added to a 350 mL thick-walled reaction bottle, and ethylene was introduced into the reactor until saturation after vacuum pumping; after pre-stirring, a dichloromethane (2 mL) solution of catalyst E-(II)-3 (10 μmol) was added and the ethylene pressure was adjusted to 0.4 MPa, and the reaction was stirred for 180 min. After the reaction was completed, the mixture was dried at 50 ° C in vacuum until constant weight to obtain a polymerization product. The specific results are shown in Table 12.

[0272] Application Example 27

[0273] The experimental process is the same as that of Application Example 26, except that the added catalyst E-(II)-3 needs to be added to the reaction system after 365nm ultraviolet irradiation for 5 minutes. The specific experimental results are shown in Table 12.

[0274] Table 12

[0275]

[0276] Application Examples 26-27 demonstrate the catalytic performance of E-(II)-3 catalyst at room temperature under a pressure of 0.4 MPa and a reaction time of 180 min. Compared with the case without illumination, E-(II)-3 catalyst exhibits relatively higher activity and molecular weight after illumination, which may be due to the weak interaction between the benzene ring on the ligand and the metal palladium, resulting in a decrease in the transfer rate, an increase in the molecular weight, and a decrease in the degree of branching.

[0277] The above 27 application examples are ethylene homopolymerization.

[0278] Application Examples 28 to 39 show that the imine nickel complex E-(I)-5 exhibits different activities and insertion rates in the copolymerization of ethylene and polar monomers.

[0279] Application Examples 28-33

[0280] According to the attached Figure 4The results of the UV-visible absorption spectrum showed that the E-(I) catalyst showed a stable state after being irradiated with 365nm UV light for 420 seconds, and there was no conversion from the E-configuration to the Z-configuration. In addition, since the concentration of the catalyst required for the copolymerization reaction was relatively high, the illumination time of the catalyst before polymerization was determined to be 20 minutes.

[0281] Under the anhydrous and oxygen-free conditions of the glove box, polar monomers of enols, anhydrous toluene and AlEt2Cl (5mL, 1M in toluene) were added to a 350mL thick-walled reaction bottle in sequence. The pressure bottle was taken out of the glove box and connected to the ethylene gas line to evacuate and then ethylene was introduced to saturation. After stirring for 10 minutes at 0.2MPa and room temperature, a dichloromethane (2mL) solution of α-diimine nickel complex E-(I)-5 (10μmol) without light or with light for 20 minutes was added and stirred for 30 minutes. After the reaction was completed, the reaction was terminated with ethanol containing 5% hydrochloric acid. After precipitation, filtration and washing, the polymer was vacuum dried at 50°C to constant weight to obtain a polymerization product. The specific experimental results are shown in Table 13.

[0282] Table 13

[0283]

[0284]

[0285] Application Examples 28 to 33 demonstrate the performance of the E-(I)-5 catalyst in catalyzing the copolymerization of ethylene and enol polar monomers at room temperature at a pressure of 0.2 MPa and a reaction time of 30 min. Compared with Applications 28 and 29, since the polar monomer is Lewis basic and the metal complex is Lewis acidic, the E-(I)-5 nickel catalyst shows deactivation results as the concentration of the polar monomer increases. However, as in Examples 29 and 30, the E-(I)-5 catalyst partially converts from the E-form to the Z-form configuration after illumination, and there is a weak interaction between the hydrogen on the ether chain of the Z-form catalyst and the bromine atom connected to the metal nickel. This characteristic makes the probability of poisoning and deactivation lower when copolymerizing with polar monomers, thereby showing activity.

[0286] Application Examples 34-39

[0287] The operation is the same as that of Application Examples 28 to 33, except that the polar monomer of the enol type is replaced by the polar monomer of the olefinic acid type, as shown in Table 14.

[0288] Table 14

[0289]

[0290] The experimental results show that: Application Examples 34 to 39 demonstrate the copolymerization performance of E-(I)-5 catalyst with ethylene and different olefinic polar monomers at room temperature at a pressure of 0.2 MPa and a reaction time of 30 min. The polymer results are consistent with the analysis in Table 13.

[0291] The nickel complex provided by the present invention can realize catalyst-catalyzed homopolymerization of ethylene or copolymerization with polar monomers, and can realize controllable catalytic activity under ultraviolet light, and can produce polyolefin materials with adjustable molecular weight and polar monomer insertion rate.

[0292] The foregoing is merely a specific embodiment of the present invention, which enables those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features claimed herein.

Claims

1. Preparation of photoresponsive mononuclear imine nickel / palladium complexes of ultra-high molecular weight polyethylene having formula E-(I), Z-(I), E-(II) And the chemical structure shown in Z-(II): Where R 1 is one of hydrogen, cyano, OCH2CH2OCH3, and substituted phenyl; R 2 is one of hydrogen, halogen, and alkoxy; M is one of metal Ni or Pd; The imine type nickel / palladium complex can undergo configuration conversion under the irradiation of ultraviolet light of two different wavelengths, converting from the trans configuration (E) to the cis configuration (Z) under the irradiation of 365nm ultraviolet light, and converting from the cis configuration (Z) to the trans configuration (E) under the irradiation of 405nm ultraviolet light.

2. The photoresponsive mononuclear imine nickel / palladium complex for preparing ultra-high molecular weight polyethylene according to claim 1, characterized in that: The α-diimine nickel / palladium complex of the chemical structure shown in formula E-(I) includes at least one of E-(I)-1 to E-(I)-5, the pyridine imine nickel / palladium complex of the chemical structure shown in formula E-(II) includes at least one of E-(II)-1 to E-(II)-3, the α-diimine nickel / palladium complex of the chemical structure shown in formula Z-(I) includes at least one of Z-(I)-1 to Z-(I)-5, and the pyridine imine nickel / palladium complex of the chemical structure shown in formula Z-(II) includes at least one of Z-(II)-1 to Z-(II)-3:

3. The method for preparing a light-responsive mononuclear imine nickel / palladium complex for preparing ultra-high molecular weight polyethylene according to claim 1 or 2, characterized in that: The following steps are involved: a. The compound represented by formula E-1 or Z-1 is subjected to Suzuki coupling reaction with compound 5 at 80-120° C. under the catalysis of a second catalyst to generate an aniline compound represented by formula E-2 or Z-2; the compound represented by formula E-2 or Z-2 is subjected to Suzuki coupling reaction with compound 6 at 80-120° C. under the catalysis of a second catalyst to generate an aniline compound represented by formula E-3 or Z-3; compound 7 is subjected to condensation reaction with an aniline compound represented by formula E-3 or Z-3 under the catalysis of a third catalyst at 80-120° C. to generate an α-diimine compound represented by formula E-4 or Z-4; b. The α-diimine compound represented by formula E-4 or Z-4 is reacted with (DME)NiBr2 or (COD)PdMeCl at 0-45° C. to generate an α-diimine nickel / palladium complex having a chemical structure represented by formula E-(I) or Z-(I); The reaction route is as follows: Among them, R 1 is one of hydrogen, cyano, OCH2CH2OCH3, substituted phenyl, R 2 is one of hydrogen, halogen, and alkoxy; The second catalyst is tetrakis(triphenylphosphine)palladium or 1,1'-bis(diphenylphosphino)ferrocenepalladium(II) dichloride; The third catalyst is zinc dichloride or p-toluenesulfonic acid.

4. The synthesis method according to claim 3, characterized in that: The molar ratio of the compound represented by formula E-1 or Z-1 to compound 5 is (1-2):1; the molar ratio of the compound represented by formula E-2 or Z-2 to compound 6 is (1-2):1; the molar ratio of compound 7 to the compound represented by formula E-3 or Z-3 is (1-2):1; the molar ratio of the compound represented by formula E-4 or Z-4 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1-6).

5. The method for synthesizing a light-responsive mononuclear imine nickel / palladium complex for preparing ultra-high molecular weight polyethylene according to claim 1 or 2, characterized in that: The following steps are involved: a. allowing compound 9 to undergo a condensation reaction with the compound represented by formula E-3 or Z-3 at 80 to 120° C. under the catalysis of a fourth catalyst to generate a pyridine imine compound represented by formula E-8 or Z-8; b. reacting the pyridine imine compound represented by formula E-8 or Z-8 with (DME)NiBr2 or (COD)PdMeCl at 0-45°C to generate a pyridine imine nickel / palladium complex having a chemical structure represented by formula E-(II) and Z-(II); The reaction route is as follows: Among them, R 1 It is one of hydrogen, cyano, OCH2CH2OCH3, and substituted phenyl. The fourth catalyst is zinc dichloride or p-toluenesulfonic acid.

6. The synthesis method according to claim 5, characterized in that: The molar ratio of compound 9 to the compound represented by formula E-3 or Z-3 is (1-2):1; the molar ratio of the compound represented by formula E-8 or Z-8 to (DME)NiBr2 or (COD)PdMeCl is 1:(0.1-6).

7. Use of the light-responsive mononuclear nickel / palladium complex for preparing ultra-high molecular weight polyethylene according to claim 1 or 2 in catalytic synthesis of polyolefin materials, characterized in that: A catalytic amount of a photoresponsive nickel / palladium complex is added as a catalyst to an olefin polymerization system, and a polymerization reaction is carried out at a temperature of 0°C to 150°C. For an ethylene homopolymerization system, a terminal olefin-containing compound is contacted with an imine nickel / palladium complex having a chemical structure shown in formula E-(I) or E-(II), an alkyl aluminum or a sodium borate reagent, and the terminal olefin-containing compound undergoes a homopolymerization reaction under the catalytic action of the catalyst. The homopolymerization reaction is carried out in an organic solvent, and the amount of the imine nickel / palladium complex used is 5 to 40 μmol·L -1 The homopolymerization temperature is 0-150°C, the pressure is 0.1-2.0 MPa, and the reaction time is 0.05-3.00 h. For the ethylene copolymerization system, the terminal olefinic compound and the polar monomer are contacted with the imine nickel / palladium complex having the chemical structure shown in formula E-(I) or E-(II) and an alkyl aluminum or sodium borate reagent, and the terminal olefinic compound and the polar monomer undergo copolymerization reaction. The copolymerization temperature is 0-50°C, the copolymerization pressure is 0.1-1.0 MPa, and the reaction time is 0.05-3.00 h. The concentration of the imine nickel / palladium complex is 200-400 μmol·L -1 , the monomer concentration is 0.1 to 3.0 M; the polar monomer refers to an α-olefin containing a heteroatom, including at least one of 10-undecenoic acid methyl ester, vinyltrimethoxysilane, 6-chloro-1-hexene, 10-undecenol, methyl acrylate, propylene acetate, and methyl norbornene.

8. The use according to claim 7, characterized in that: Before adding a catalytic amount of the photoresponsive nickel / palladium complex into the olefin polymerization system, E-(I) or E-(II) is irradiated with ultraviolet light, wherein the wavelength of the ultraviolet light is 365 nm.

9. The use according to claim 8, characterized in that: With the help of ultraviolet light irradiation, the ratio between the E-configuration and the Z-configuration of the photoresponsive nickel complex can be precisely controlled. When this photoresponsive nickel complex is used as a catalyst, the reaction rate in the olefin polymerization process can be adjusted, thereby achieving effective control of the molecular weight of the polyolefin material and the insertion rate of the polar monomer.

10. The use according to claim 7, characterized in that: The complex is used as an ultra-high activity and high thermal stability catalyst to catalyze ethylene polymerization to prepare an ultra-high molecular weight polyethylene thermoplastic elastomer, wherein the ultra-high molecular weight polyethylene has a molecular weight distribution of 1.60 to 2.57 and a molecular weight of 632 to 1184×10 4 g·mol -1 , and has good physical and mechanical properties, the elastic recovery rate of the product is as high as 92%.

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