Ligand compound with metal ion regulation function, catalyst, and preparation method

Abstract

The present disclosure provides a ligand compound with a metal ion regulation function, a catalyst, and a preparation method, belonging to the technical field of organic synthesis. The ligand compound with a metal ion regulation function includes the structure shown in formula (I): #imgabs0# where Ar1 and Ar2 are each independently selected from any one of a substituted phenyl group and a substituted naphthyl group and are different from each other. The substituted phenyl group has at least one ferrocene substituent, an azobenzene substituent, or a cyano substituent, and the substituted naphthyl group has at least one phenyl substituent substituted with a carboxyl group.

Description

Technical Field

[0001] The present disclosure belongs to the technical field of organic synthesis, and particularly relates to a ligand compound with a metal ion regulation effect, a catalyst, and a preparation method thereof. Background Art

[0002] Polyethylene is one of the most widely used and superior synthetic plastics to date. The non-polar nature of traditional polyethylene materials limits their properties such as dyeability and processability. Preparing polar polyethylene is one of the effective strategies to solve the above problems. Most polar polyethylenes are prepared by coordination polymerization, so developing coordination polymerization catalysts with excellent performance is the key in this field.

[0003] Most coordination polymerization catalysts regulate their performance through electronic and steric effects. In recent years, the regulation of polymerization by external stimuli has developed rapidly. As a method for regulating the microstructure of polymers, it has shown great potential. Using external stimuli to regulate the microstructure such as the molecular weight and degree of branching of polymers is more convenient and feasible than traditional synthesis methods. In this field, different external stimulus methods can induce the olefin polymerization process. However, currently, most studies mainly focus on unilateral external stimuli, and there are fewer studies on achieving dual external stimuli in the same reaction system. Summary of the Invention

[0004] In view of the above technical problems, the present disclosure provides a ligand compound with a metal ion regulation effect, a catalyst, a preparation method, and an application thereof, in order to at least partially solve the above technical problems.

[0005] As the first aspect of the present disclosure, there is provided a ligand compound with a metal ion regulation effect, including the structure shown in formula (I):

[0006]

[0007] Wherein, Ar1 and Ar2 are each independently selected from any one of a substituted phenyl group and a substituted naphthyl group and are different from each other. The substituted phenyl group has at least one ferrocene substituent, an azobenzene substituent, or a cyano substituent, and the substituted naphthyl group has at least one phenyl substituent substituted with a carboxyl group.

[0008] As the second aspect of the present disclosure, there is provided a method for preparing a ligand compound with a metal ion regulation effect, including:

[0009] Reacting compound A, Ar1-NH2, with compound B to obtain compound C and then reacting with compound D, Ar2-NH2, to obtain the ligand compound shown in formula (I).

[0010] As the third aspect of the present disclosure, a palladium compound is provided, which is obtained by reacting the above ligand compound with a metal palladium precursor. Among them, the structure of the palladium compound is shown in Formula (II):

[0011]

[0012] As the fourth aspect of the present disclosure, a method for preparing a palladium compound is provided, including:

[0013] Adding a metal palladium precursor to an organic solution of the ligand compound shown in Formula (I), and reacting to obtain the compound shown in Formula (II),

[0014] Wherein:

[0015] The solvent of the organic solution includes dichloromethane;

[0016] The metal palladium precursor includes chloro(1,5-cyclooctadiene)methylpalladium;

[0017] The molar ratio of the ligand compound to the metal palladium precursor is 1:1 to 1:1.2;

[0018] The reaction time is 12 - 24 h.

[0019] As the fifth aspect of the present disclosure, a diimine palladium catalyst is provided, including:

[0020] The palladium cation compound shown in Formula (III):

[0021]

[0022] Or the oxide shown in Formula (IV):

[0023]

[0024] Among them, the palladium cation compound shown in Formula (III) is obtained by reacting the palladium compound shown in Formula (II) with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and the oxide shown in Formula (IV) is obtained by reacting the palladium cation compound shown in Formula (III) with silver tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0025] As the sixth aspect of the present disclosure, a diimine catalyst with a metal ion regulating effect is provided, including:

[0026] The palladium cation compound shown in Formula (III) or the oxide shown in Formula (IV), and a metal cation combined with a carboxyl group;

[0027] The metal cation includes Na + 、K + 、Mg 2+, Fe 3+ , Ti 4+ Any one of;

[0028] Among them, the diimine catalyst with metal ion regulation effect is obtained by reacting a palladium cationic compound shown in formula (III) or an oxide shown in formula (IV) with a metal salt.

[0029] As the seventh aspect of the present disclosure, a method for polyolefins is provided, including:

[0030] Under optional preset conditions, using the above-mentioned diimine palladium catalyst or the above-mentioned diimine catalyst with metal ion regulation effect to catalyze the homopolymerization reaction of olefins; or

[0031] Using the above-mentioned diimine palladium catalyst or the above-mentioned diimine catalyst with metal ion regulation effect to catalyze the copolymerization reaction of olefins and polar monomers;

[0032] Among them, the optional preset conditions include at least one of the following:

[0033] Ultraviolet and visible light illumination, using Lewis acid additives.

[0034] The ligand compound, catalyst, and preparation method provided by the present disclosure with metal ion regulation effect have at least one of the following beneficial effects:

[0035] (1) According to the embodiments of the present disclosure, the ligand compound with metal ion regulation effect provided by the present disclosure contains two or more different substituents. Among them, the carboxyl substituent in the ligand compound can coordinate with metals of different valence states to regulate the composition state of the catalyst, while other substituents in the ligand compound can regulate the electronic effect in the catalyst under external stimuli, thereby realizing the dual response of the catalyst.

[0036] (2) According to the embodiments of the present disclosure, in the process of catalyzing the synthesis of polyolefins by the diimine palladium catalyst and the catalyst with metal ion regulation effect composed of ligand compounds provided in the embodiments of the present disclosure, different stimulus-responsive substituents in the ligand compound are used, and they can dynamically regulate the yield, molecular weight, and degree of polymerization of polyolefins under different external stimuli.

[0037] (3) According to the embodiments of the present disclosure, the ligand compounds provided by the present disclosure have redox regulation ability. By using the ferrocene substituents in the ligand compounds, under the stimulation of the external oxidant AgBAF, the divalent iron in ferrocene can be converted into trivalent iron. After oxidation, ferrocene reduces the electron cloud density of the palladium metal center, making it more electrophilic. In addition, the oxidized ferrocene by AgBAF also has reversible reducibility. Moreover, the oxides provided by the present disclosure also have metal ion regulation effect. By using the carboxyl substituents in the ligand compounds, they can react with metal salts to obtain a carboxylic acid-metal ion regulation unit, thereby achieving regulation. The ligand compounds provided by the present disclosure also have light regulation and Lewis acid regulation. By using the azobenzene substituents in the ligand compounds, the cis and trans structures of the ligand compounds can be regulated under ultraviolet light and visible light illumination; by using the cyano groups in the ligand compounds, they can coordinate with Lewis acids to achieve regulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1A 1H NMR spectrum of compound (2) in Example 1 of the present disclosure;

[0039] Figure 1B 13C NMR spectrum of compound (2) in Example 1 of the present disclosure;

[0040] Figure 2A 1H NMR spectrum of compound (5) in Example 1 of the present disclosure;

[0041] Figure 2B 13C NMR spectrum of compound (5) in Example 1 of the present disclosure;

[0042] Figure 3A 1H NMR spectrum of compound (I) in Example 1 of the present disclosure;

[0043] Figure 3B 13C NMR spectrum of compound (I) in Example 1 of the present disclosure;

[0044] Figure 4A 1H NMR spectrum of compound (II) in Example 2 of the present disclosure;

[0045] Figure 4B 13C NMR spectrum of compound (II) in Example 2 of the present disclosure;

[0046] Figure 5 Schematic diagram of the single crystal structure of compound (II) in Example 2 of the present disclosure;

[0047] Figure 6 Cyclic voltammogram curves of different compounds in the examples of the present disclosure;

[0048] Figure 71H NMR spectra of the compound of formula (III) before and after adding an oxidizing agent and a reducing agent according to an embodiment of the present disclosure. Detailed implementation manners

[0049] To make the objectives, technical solutions and advantages of the present disclosure more clear and understandable, the following further describes the present disclosure in detail with reference to specific embodiments and the accompanying drawings.

[0050] In view of the current situation where only single - stage catalytic regulation of polyolefins can be achieved, the present disclosure realizes multiple response regulations during the preparation of polyolefins by introducing two or more different substituents into the same compound.

[0051] Specifically, in the first aspect of the present disclosure, a ligand compound with a metal ion regulation effect is provided, including the structure shown in formula (I):

[0052]

[0053] Wherein, Ar1 and Ar2 are each independently selected from any one of a substituted phenyl group and a substituted naphthyl group and are different from each other. The substituted phenyl group has at least one ferrocene substituent, an azobenzene substituent or a cyano substituent, and the substituted naphthyl group has at least one phenyl substituent substituted with a carboxyl group.

[0054] In the embodiments of the present disclosure, the ligand compound provided by the present disclosure contains two or more different substituents. Among them, the carboxyl substituent in the ligand compound can coordinate with metals of different valence states to regulate the composition state of the catalyst, and other substituents in the ligand compound can regulate the electronic effect in the catalyst with a metal ion regulation effect under external stimuli, thereby achieving dual responses.

[0055] According to the embodiments of the present disclosure, the substituted phenyl group further includes at least one substituent selected from benzhydryl, isopropyl, methyl, tert - butyl, and phenyl; and / or the substituted naphthyl group further includes at least one substituent selected from isopropyl substituted with diphenyl, isopropyl, methyl, tert - butyl, and phenyl.

[0056] For example, the ligand compound with the structure shown in formula (I) above includes, but is not limited to, the following specific compounds:

[0057]

[0058] According to the embodiments of the present disclosure, taking the substituent of the substituted phenyl group as an isopropyl group and a ferrocene substituent, and the substituent of the substituted naphthyl group as a phenyl substituent substituted with a carboxyl group as an example, the specific structure of the ligand compound shown in formula (I) is as shown in formula (I):

[0059]

[0060] In an embodiment of the present disclosure, the ligand compound represented by formula (I) contains both a ferrocene substituent and a carboxyl substituent, and these two groups can exhibit dual responses under external stimuli (such as redox, metal salt ions). It should be noted that the phenyl group substituted with a carboxyl group can also be combined with substituents of other groups, not limited to the ferrocene substituent.

[0061] According to an embodiment of the present disclosure, a second aspect of the present disclosure provides a method for preparing a ligand compound having a metal ion regulation effect, including:

[0062] Reacting compound A, Ar1-NH2, with compound B to obtain compound C and then reacting with compound D, Ar2-NH2, to obtain the ligand compound represented by formula (I).

[0063] Specifically, the reaction process for preparing the ligand compound having a metal ion regulation effect is as follows:

[0064]

[0065] According to an embodiment of the present disclosure, the method for preparing the ligand compound having a metal ion regulation effect in the above embodiment includes:

[0066] Adding compound B and an organic acid catalyst to an organic solution of compound A, reacting at a preset temperature to obtain compound C; adding compound C and an organic acid catalyst to an organic solution of compound D, reacting at a preset temperature to obtain the ligand compound represented by formula (I). Among them, the organic solution is selected from methanol, and the organic acid catalyst is selected from any one of formic acid and acetic acid. The preset reaction temperature is 25°C - 80°C, such as 25°C, 40°C, 80°C, etc.; the reaction time is 24h - 48h, such as 24h, 36h, 48h, etc.

[0067] For example: adding compound B and formic acid to a methanol solution of compound A in sequence, reacting at the preset reaction temperature for 48h, filtering and separating the generated solid, washing the solid three times with methanol, and drying it under vacuum to obtain compound C. Then, adding compound C and formic acid to a methanol solution of compound D in sequence, reacting at the preset reaction temperature for 48h, filtering and separating the generated solid, dissolving the solid, and performing column chromatography separation to obtain the ligand compound represented by formula (I).

[0068] According to an embodiment of the present disclosure, compound B has a molar ratio of 3 - 5:1 to compound A, Ar1-NH2, for example, the molar ratio is 5:1; compound D, Ar2-NH2, and compound C The molar ratio is 1 to 2:1, for example, the molar ratio is 1.5:1. The excess B compound and D compound contribute to the formation of the ligand compound shown in formula (I).

[0069] According to an embodiment of the present disclosure, a third aspect of the present disclosure provides a palladium compound, which is obtained by reacting the ligand compound shown in formula (1) in the above embodiment with a metal palladium precursor, wherein the structure of the palladium compound is shown in formula (II):

[0070]

[0071] Specifically, taking the reaction of the ligand compound shown in formula (I) with the metal palladium precursor as an example, the specific structure of the obtained palladium compound is shown in formula (II):

[0072]

[0073] According to an embodiment of the present disclosure, a fourth aspect of the present disclosure provides a method for preparing the palladium compound in the above embodiment, including: adding a metal palladium precursor to an organic solution of the ligand compound shown in formula (I) to react to obtain a compound shown in formula (II), wherein the solvent of the organic solution includes dichloromethane; the metal palladium precursor includes chloro(1,5-cyclooctadiene)methylpalladium ((COD)PdMeCl); the molar ratio of the ligand compound to the metal palladium precursor is 1:1 to 1:1.2, for example, the molar ratio of the ligand compound of formula (I) to the metal palladium precursor is 1:1.

[0074] For example: In a glove box, (COD)PdMeCl is added to a dichloromethane solution dissolving the compound shown in formula (I) and reacted for 12 to 24 h. The solvent is dried under vacuum, and the required compound is separated by column chromatography to obtain an orange solid, that is, the palladium compound shown in formula (II) is obtained.

[0075] According to an embodiment of the present disclosure, a fifth aspect of the present disclosure provides a diimine palladium catalyst, including: a palladium cation compound shown in formula (III):

[0076]

[0077] Or an oxide shown in formula (IV):

[0078]

[0079] According to an embodiment of the present disclosure, the palladium cation compound shown in formula (III) is obtained by reacting the palladium compound shown in formula (II) with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBAF), wherein the molar ratio of the palladium compound shown in formula (II) to NaBAF is 1:1 to 1:1.2, preferably 1:1.

[0080] Specifically, the method for preparing the palladium cation compound shown in the above formula (III) includes: dissolving the palladium cation compound shown in formula (II) in an acetonitrile solution, then adding NaBAF, and reacting for 12 to 24 hours. After removing impurities (sodium chloride) through diatomaceous earth, collecting the filtrate, drying the solvent, adding n-hexane solvent in a glove box, stirring for 10 to 15 minutes, and filtering to obtain a dark red solid, that is, the palladium cation compound shown in the structural formula (III) is obtained.

[0081] For example: taking the reaction of the palladium compound shown in formula (II) with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBAF) to obtain the diimine palladium cation compound with the specific structure shown in formula (III) as an example, the specific structure of the compound shown in formula (III) is as follows:

[0082]

[0083] According to an embodiment of the present disclosure, the oxide shown in formula (IV) is obtained by reacting the palladium cation compound shown in formula (III) with silver tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (AgBAF), wherein the molar ratio of the palladium cation compound shown in formula (III) to AgBAF is 1:1 to 1:1.2, preferably 1:1.

[0084] Specifically, the method for preparing the oxide shown in the above formula (IV) includes: in a glove box, adding AgBAF to the dichloromethane solution dissolving the palladium cation compound shown in formula (III), and reacting for 1 to 2 hours. Filtering to remove the by-product silver chloride through diatomaceous earth, collecting the filtrate, drying the solvent, and directly obtaining a dark red solid, that is, the oxide shown in the structural formula (IV) is obtained.

[0085] For example: taking the reaction of the compound shown in the structural formula (III) with AgBAF to obtain the oxide of the palladium cation compound with the specific structure shown in formula (IV) as an example, the specific structure shown in formula (IV) is as follows:

[0086]

[0087] In an embodiment of the present disclosure, when AgBAF is added, the ferrocene unit in the compound shown in formula (III) or (III) is oxidized. After oxidation, the electron-withdrawing effect of the ferrocene unit shown in formula (IV) or (IV) is stronger, which can reduce the electron cloud density of the palladium metal center, making the compound shown in formula (IV) or (IV) more electrophilic and more likely to undergo β-H elimination during the polymerization of polyolefins, that is, the chain transfer rate is increased, so the activity is reduced, and the molecular weight of the obtained polymer is reduced while the degree of branching is increased.

[0088] According to an embodiment of the present disclosure, a sixth aspect of the present disclosure provides a diimine catalyst having a metal ion regulating effect, including: a palladium cation compound represented by formula (III) or an oxide represented by formula (IV), and a metal cation bonded to a carboxyl group; the metal cation includes Na + , K + , Mg 2+ , Fe 3+ , Ti 4+ any one of them.

[0089] According to an embodiment of the present disclosure, the diimine catalyst having a metal ion regulating effect is obtained by reacting a palladium cation compound represented by formula (III) or an oxide represented by formula (IV) with a metal salt; wherein, the metal salt includes any one of NaH, KH, MgCl2, FeCl3, TiCl4, and the molar ratio of the palladium cation compound represented by formula (III) or the oxide represented by formula (IV) to the metal salt is 1:2 to 3, preferably 1:2.

[0090] Specifically, the method for preparing the diimine palladium catalyst containing the palladium cation compound represented by formula (III) includes: in a glove box, adding a metal salt to a dichloromethane solution dissolving the palladium cation compound represented by structural formula (III), and reacting for 3 to 6 h. Filter off the insoluble matter with diatomaceous earth, collect the filtrate, dry the solvent, and directly obtain a dark red solid, thus obtaining the diimine catalyst with a metal ion regulating effect having the structure of formula (III).

[0091] For example: taking the reaction of the compound represented by structural formula (III) with NaH in dichloromethane to obtain a diimine palladium catalyst having a sodium ion regulating effect as an example, the specific structure of the obtained diimine palladium catalyst is as shown in formula (V):

[0092]

[0093] Specifically, the method for preparing the diimine palladium catalyst containing the oxide represented by formula (IV) includes: in a glove box, adding a metal salt to a dichloromethane solution dissolving the oxide represented by structural formula (IV), and reacting for 3 to 6 h. Filter off the insoluble matter with diatomaceous earth, collect the filtrate, dry the solvent, and directly obtain a dark red solid, thus obtaining the diimine catalyst with a metal ion regulating effect having the structure of formula (IV).

[0094] For example: taking the reaction of the compound represented by structural formula (IV) with NaH in dichloromethane to obtain a palladium catalyst having sodium ions as an example, its exemplary structural formula (VI) is as follows:

[0095]

[0096] In an embodiment of the present disclosure, after adding different metal salts to the compound shown in formula (III) or formula (IV), the carboxyl unit reacts with different metal ions, and through the metal-metal interaction between the palladium metal center and the metal ions, the polymerization activity is improved, and the polymer molecular weight of the obtained polyolefin is also increased.

[0097] According to an embodiment of the present disclosure, a seventh aspect of the present disclosure provides a method for preparing polyolefin, including: using the diimine catalyst with a metal ion regulating effect in the above embodiment as a catalyst, and preparing polyolefin through a polymerization reaction, wherein the polymerization reaction includes: a homopolymerization reaction and a copolymerization reaction.

[0098] Specifically, under optional preset conditions, the homopolymerization reaction of olefins is catalyzed by the diimine palladium catalyst in the above embodiment or the diimine catalyst with a metal ion regulating effect in the above embodiment; or the copolymerization reaction of olefins and polar monomers is catalyzed by the diimine palladium catalyst in the above embodiment or the diimine catalyst with a metal ion regulating effect in the above embodiment.

[0099] According to an embodiment of the present disclosure, the olefins include ethylene, propylene, etc.; the polar monomers include at least one of allylic polar monomers, long-chain polar monomers, and norbornene monomers. The allylic polar monomers include, but are not limited to, methyl acrylate; the long-chain polar monomers include, but are not limited to, methyl 10-undecenoate, and the norbornene monomers include, but are not limited to, norbornene.

[0100] According to an embodiment of the present disclosure, the reaction temperature is 0-60°C, such as 20°C, 40°C, 60°C, etc.

[0101] According to an embodiment of the present disclosure, the optional preset conditions include at least one of the following: ultraviolet and visible light illumination, using a Lewis acid additive.

[0102] According to an embodiment of the present disclosure, the above palladium compound is used as a catalyst to participate in the polymerization reaction for preparing polyolefin. Through the oxidation of the ferrocene unit in the catalyst by AgBAF, the carboxyl unit reacts with different metal ions, and then the olefin polymerization process is regulated by using an oxidation-reduction agent and metal ions simultaneously, so as to obtain polyolefins with different molecular weights, thereby realizing the means of dual regulation of the olefin polymerization reaction by the oxidation-reduction agent and metal ions.

[0103] According to an embodiment of the present disclosure, when the diimine palladium catalyst or the diimine catalyst having a metal ion regulating effect (i.e., the compounds shown in Formula (III) and Formula (IV)) contains an azobenzene substituent, when irradiated with light of 365 nm, due to the π-π* transition of the azobenzene group, the compounds shown in the above Formula (III) and Formula (IV) have a strong absorption value at 365 nm. As time goes by, the π-π* absorption of the trans isomers of the compounds shown in Formula (III) and Formula (IV) gradually decreases, and the cis isomers are formed; when irradiated with a light source of 420 nm wavelength, as time changes, the π-π * absorption increases, and the compounds shown in the above Formula (III) and Formula (IV) are converted from the cis structural isomers to the trans isomers again.

[0104] According to an embodiment of the present disclosure, when the diimine palladium catalyst or the diimine catalyst having a metal ion regulating effect (i.e., the compounds shown in Formula (III) and Formula (IV)) contains a cyano substituent, the cyano substituent can coordinate with a Lewis acid additive to thereby regulate the polymerization reaction of polyolefins, wherein the Lewis acid additive can be selected from tris(pentafluorophenyl)borane (B(C6F5)3).

[0105] The ligand compounds, catalysts and applications provided by the present disclosure will be described in detail below in conjunction with specific embodiments and drawings.

[0106] Examples

[0107] Example 1

[0108] The route for synthesizing compound (2) for preparing the ligand compound shown in Formula (I) is shown in Formula (VII):

[0109]

[0110] Specific method for synthesizing compound (2): Under N2 condition at -20 °C, add a hexane solution of n-butyllithium (12.0 mL, 2.5 M, 30 mmol) to a solution of ferrocene (2.23 g, 12 mmol) in tetrahydrofuran (100 mL), stir for 1 h, warm up to room temperature and stir for 1 h, add a solution of ZnCl2 (1.63 g, 12 mmol) in tetrahydrofuran (10 mL) and stir for 1 h, add a solution of 2,6-diisopropyl-4-bromoaniline (2.23 g, 10 mmol) and Pd(PPh3)4 (116 mg, 1 mmol) in tetrahydrofuran (10 mL), warm up to 90 °C and react for 12 h. Filter to remove insoluble substances, extract with ethyl acetate, dry over Na2SO4, and separate by column chromatography to obtain the target product (1). Charge compound (1) (1.80 g, 5.0 mmol), 2,3-butanedione (2.15 g, 25.0 mmol), a catalytic amount of formic acid and methanol (50 mL) into a 100 mL round-bottom flask. After stirring at 40 °C for 24 h, separate the resulting solid by filtration, wash it three times with methanol, and dry it under vacuum to obtain the orange solid compound (2) (1.70 g, 78%).

[0111] The structure of compound (2) was characterized by 1 1H NMR spectrum, 13 13C NMR spectrum, and the specific results are as shown in Figure 1A 、 Figure 1B shown.

[0112] 1 1H NMR (400 MHz, C6D6) δ 7.45 (s, 2H), 4.58 (t, J = 1.6 Hz, 2H), 4.16 (t, J = 1.6 Hz, 2H), 3.99 (s, 5H), 2.65–2.52 (m, 2H), 2.40 (s, 3H), 1.74 (s, 3H), 1.14 (dd, J = 16.0, 8.0 Hz, 12H).

[0113] 13 13C NMR (101 MHz, C6D6) δ 197.65, 166.18, 142.80, 134.57, 133.71, 120.78, 86.44, 68.75, 67.73, 66.01, 27.60, 23.44, 22.18, 21.61, 13.89. HRMS (m / z): calcd for C 26 19 31 H

[0114] The reaction route for synthesizing compound (3) is shown in Scheme (VIII):

[0115]

[0116] Specific method for synthesizing compound (3): Under N2 condition, dissolve 1-naphthylamine (1.43 g, 10 mmol), 2-pyridinecarboxylic acid (1.35 g, 11 mmol), and 4-methylaminopyridine (122 mg, 1 mmol) in dichloromethane with stirring. At 0 °C, add a dichloromethane solution of N,N'-dicyclohexylcarbodiimide (2.10 g, 11 mmol), and stir at room temperature for 12 h. Filter to remove insoluble substances, extract with water, dry over Na2SO4, evaporate to dryness, and separate by column chromatography to obtain the target product (3).

[0117] The reaction route for synthesizing compound (5) is shown in Formula (IX):

[0118]

[0119] Specific method for synthesizing compound (5): Under N2 condition, react a mixture of compound (3) (6.7 g, 27 mmol), 4-iodobenzonitrile (22.9 g, 81 mmol), AgOAc (6.7 g, 40.5 mmol), and Pd(OAc)2 (160 mg, 0.68 mmol) at 140 °C for 24 h, and separate by column chromatography to obtain compound (4). Reflux compound (4) (6.4 g, 15 mmol) in NaOH solution (6.0 g NaOH, 150 mmol in EtOH / H2O, 10 / 1, v / v, 60 mL) for 18 h. After the reaction is completed, evaporate ethanol, extract with dichloromethane, dry over Na2SO4, and separate by column chromatography to obtain compound (5).

[0120] The structure of compound (5) was characterized by 1 1H NMR spectrum, 13 13C NMR spectrum, as shown in Figure 2A 、 Figure 2B shown below.

[0121] 1 1H NMR (400 MHz, DMSO-d6) δ 8.03 (d, J = 8.0 Hz, 2H), 7.82 (dd, J = 8.2, 1.3 Hz, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.41 (dd, J = 8.2, 7.0 Hz, 1H), 7.32–7.21 (m, 2H), 7.10 (dd, J = 7.0, 1.3 Hz, 1H), 6.70 (dd, J = 6.8, 2.0 Hz, 1H), 4.44 (s, 2H).

[0122] 1313C NMR (101 MHz, DMSO) δ 167.59, 147.84, 145.00, 137.65, 135.97, 130.14, 129.72, 129.36, 129.30, 128.05, 127.37, 124.84, 119.75, 117.63, 110.89.

[0123] The route for preparing the compound shown in formula (I) from compound (2) and compound (5) is as shown in formula (X):

[0124]

[0125] Specific method for synthesizing the compound of formula (I): Charge compound (2) (4.30 g, 10.0 mmol), compound (5) (2.63 g, 10.0 mmol), a catalytic amount of formic acid and methanol (50 mL) into a 100 mL round-bottom flask. Stir the resulting suspension at 40 °C for 48 hours. Separate the resulting solid by filtration, dissolve the residue in dichloromethane and perform column chromatography to obtain an orange solid as the compound shown in formula (I) (3.50 g, 56%).

[0126] The structure of the compound shown in formula (I) was characterized by 1 1H NMR spectrum,[[]]END]] 13 13C NMR spectrum, and the specific results are as shown in Figure 3A 、 Figure 3B shown.

[0127] 1 1H NMR (400 MHz, DMSO-d6) δ 8.05 (d, J = 8.3 Hz, 1H), 7.91 (d, J = 7.9 Hz, 2H), 7.85 (d, J = 8.1 Hz, 1H), 7.59 (td, J = 7.7, 2.4 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 18.4 Hz, 3H), 6.75 (d, J = 7.2 Hz, 1H), 4.82–3.85 (m, 7H), 2.41–2.27 (m, 2H), 1.99 (s, 3H), 1.19 (s, 3H), 1.12 (dd, J = 16.5, 6.8 Hz, 13H).

[0128] 1313C NMR (101 MHz, DMSO) δ 167.91, 167.88, 165.82, 148.20, 147.55, 144.26, 138.44, 135.44, 134.64, 134.03, 130.24, 129.26, 129.11, 128.75, 126.70, 125.87, 125.40, 123.40, 121.39, 116.02, 87.24, 69.76, 69.72, 68.73, 66.85, 45.71, 28.19, 23.34, 22.85, 16.72, 15.33, 10.61.

[0129] Example 2

[0130] The route for synthesizing the compound of formula (II) is shown in formula (XI):

[0131]

[0132] Specific method for synthesizing the compound of formula (II): Add compound (I) (675 mg, 1.0 mmol), (COD)PdMeCl (265 mg, 1 mmol) (COD = 1,2-dimethoxyethane) and dichloromethane (20 mL) into a 50 mL Schlenk flask. After stirring at room temperature for 12 hours. During the stirring process, the solid completely dissolves and the color of the solution changes from orange to dark red. At the end of the reaction, the solvent is removed under vacuum and the desired compound is separated by column chromatography. The product is a dark red solid, the compound shown in formula (II) (660 mg, 79%).

[0133] The structure of the compound shown in formula (II) was characterized by 1 1H NMR spectrum, 13 13C NMR spectrum, and the specific results are as shown in Figure 4A 、 Figure 4B shown.

[0134] 11H NMR (400 MHz, CDCl3) δ 8.42 (d, J = 8.1 Hz, 1H), 8.17 (dd, J = 19.0, 8.0 Hz, 2H), 7.95 (dd, J = 28.6, 8.1 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.55 (dd, J = 15.2, 7.5 Hz, 1H), 7.47 (d, J = 7.6 Hz, 1H), 7.40 (d, J = 7.3 Hz, 1H), 7.31 (s, 1H), 4.59 (s, 2H), 4.30 (s, 2H), 4.02 (s, 5H), 2.95 (t, J = 6.9 Hz, 1H), 2.22 (dt, J = 13.3, 7.1 Hz, 1H), 1.82 (s, 3H), 1.71 (s, 3H), 1.37 (dd, J = 19.0, 6.8 Hz, 5H), 1.07 (dd, J = 17.1, 6.9 Hz, 6H), 0.60 (s, 3H).

[0135] 13 13C NMR (101 MHz, DMSO) δ 167.83, 167.58, 165.81, 148.75, 147.43, 144.23, 138.26, 135.42, 134.60, 134.05, 130.24, 129.46, 129.30, 129.20, 128.78, 126.74, 125.89, 125.45, 123.38, 121.40, 116.09, 87.22, 69.85, 69.73, 68.74, 66.85, 28.19, 23.40, 23.33, 22.84, 16.77, 15.32.

[0136] Figure 5 It is a schematic diagram of the single crystal structure of the compound shown in Formula (II) in Example 2 of the present disclosure.

[0137] As Figure 5 shown in the single crystal structure diagram, it intuitively reflects the correctness of the structure of the compound shown in Formula (II), and shows the spatial structure of the compound, that is, the relative positions of the atoms.

[0138] Example 3

[0139] The synthetic route of the compound of Formula (III) is shown in Formula (XII):

[0140]

[0141] Method for synthesizing the compound of formula (III): Add NaBAF (886 mg, 1.0 mmol) and the compound of formula (II) (830 mg, 1.0 mmol) into a Schlenk flask under a nitrogen atmosphere. Add acetonitrile (15 mL) to form a bright orange solution, and stir for 12 h. Filter the solution through diatomaceous earth to remove the white NaCl precipitate. Evaporate the volatile substances to obtain the compound of formula (III) as a dark red solid (820 mg, 96%). Directly carry out polymerization and copolymerization without further purification.

[0142] Example 4

[0143] The synthetic route of the compound of formula (IV) is shown in formula (XIII):

[0144]

[0145] Method for synthesizing the compound of formula (IV): Add the compound of formula (III) (176 mg, 0.1 mmol), AgBAF (95.1 mg, 0.1 mmol) and 10 mL of CH2Cl2 into a 50 mL Schlenk flask. Stir for 1 h, filter through diatomaceous earth to remove the silver precipitate, and obtain the compound of formula (IV) (160 mg, 91%) after vacuum drying. Directly carry out polymerization and copolymerization without further purification.

[0146] Example 5

[0147] The synthetic route of the compound of formula (V) is shown in formula (XIV):

[0148]

[0149] Method for synthesizing the compound of formula (V):

[0150] Add the compound of formula (III) (176 mg, 0.1 mmol), NaH (4.8 mg, 0.2 mmol) and 10 mL of CH2Cl2 into a 50 mL Schlenk flask. Stir for 6 h, filter through diatomaceous earth to remove the precipitate, and obtain the compound of formula (V) shown in formula (XIV) (156 mg, 91%) after vacuum drying. Directly carry out polymerization and copolymerization without further purification.

[0151] Example 6

[0152] The reaction route of the compound of formula (III) with KI is shown in formula (XV):

[0153]

[0154] The synthesis method of route formula (XV) is the same as that of the above route formula (XIV).

[0155] Example 7

[0156] The reaction route of the compound shown in Formula (III) with MgCl2 is as shown in Formula (XVI):

[0157]

[0158] The synthesis method of Route Formula (XVI) includes: adding the compound of Formula (III) (178 mg, 0.1 mmol), MgCl2 (4.8 mg, 0.05 mmol) and 10 mL of CH2Cl2 into a 50 mL Schlenk flask. Stir for 6 h, filter with diatomaceous earth, remove the precipitate, and after vacuum drying, obtain the compound shown in Route Formula (XVI) (156 mg, 90%). This compound can be directly polymerized and copolymerized without further purification.

[0159] Example 8

[0160] The reaction route of the compound shown in Formula (III) with FeCl3 is as shown in Formula (XVII):

[0161]

[0162] The synthesis method of Route Formula (XVII) is the same as that of the above Route Formula (XVI), and the only difference is that MgCl2 is replaced by FeCl3.

[0163] Example 9

[0164] The reaction route of the compound shown in Formula (III) with TiCl4 is as shown in Formula (XVIII):

[0165]

[0166] The synthesis method of Route Formula (XVIII) is the same as that of the above Route Formula (XVI), and the only difference is that FeCl3 is replaced by TiCl4.

[0167] Similarly, the compound shown in Formula (IV) can also react with NaH, KH, MgCl2, FeCl3, and TiCl4, and the reaction mechanism is the same as that of the compound shown in Formula (III).

[0168] According to the embodiments of the present disclosure, the redox potentials of the compounds shown in the above Formulas (II), (III), and (IV) with AgBAF are tested. Specifically, the cyclic voltammetry data of different AgBAF with the compounds shown in Formulas (II), (III), and (IV) are shown in Table 1, and the cyclic voltammograms are as Figure 6 shown.

[0169] Table 1. Cyclic voltammetry data of AgBAF with the compounds shown in Formulas (II), (III), and (IV)

[0170] Compound <![CDATA[Ep A / V]]> <![CDATA[Ep C / V]]> <![CDATA[E 1 / 2 / V]]> <![CDATA[AgBAF b > 0.960 0.620 0.790 Pd-Cl 0.590 0.296 0.443 Pd 0.568 0.336 0.452 <![CDATA[Pd + > 0.582 0.338 0.460

[0171] Among them, Pd-Cl represents the compound shown in formula (II), Pd represents the compound shown in formula (III), and Pd + represents the compound shown in formula (IV).

[0172] As can be seen from Table 1, the E l / 2 value of AgBAF is greater than the E l / 2 values of the compounds shown in formulas (II), (III), and (IV), indicating that AgBAF can be used as an oxidant for palladium compounds (formula (II)) and diimine palladium catalysts (formulas (III) and (IV)). From Figure 6 the cyclic voltammograms of (a), (b), and (c) in it, it can be seen that the corresponding compounds shown in formulas (II), (III), and (IV) all have quasi-reversible redox peaks, indicating that they can all reversibly undergo redox reactions.

[0173] Furthermore, the present disclosure uses the palladium cation compound shown in formula (III) to conduct an external stimulus regulation experiment on redox, and the specific experimental test results are as Figure 7 shown.

[0174] Figure 7 This is the 1H nuclear magnetic resonance spectrum of the stacking of the compound shown in formula (III) in the examples of the present disclosure.

[0175] As Figure 7 shown in (a) and (b) in it, through the nuclear magnetic resonance monitoring experiment on the compound shown in formula (III), this experiment shows that adding 1 equivalent of AgBAF to the compound shown in formula (III) will cause the complete disappearance of the nuclear magnetic signal. After adding the reducing agent Cp2Co, the nuclear magnetic resonance signal reappears again, as Figure 7 shown in (c) in it. The main reason is that after adding the oxidant AgBAF, ferrocene is oxidized, and iron changes from divalent to trivalent. Therefore, Fe has paramagnetism, resulting in the disappearance of the peaks in the nuclear magnetic spectrum; while after adding the reducing agent Cp2Co, the paramagnetic trivalent iron is reduced, and the peaks in the nuclear magnetic spectrum can reappear. Among them, Pd represents the palladium cation compound of formula (III), Pd + 1eq.AgBAF represents adding 1 equivalent of the AgBAF oxidant to the compound shown in formula (III), and Pd + + 1eq Cp2Co represents adding 1 equivalent of the reducing agent Cp2Co to the oxide shown in formula (IV)

[0176] According to the embodiments of the present disclosure, there is also provided a method for catalyzing the polymerization reaction of olefins by using the compounds in the above embodiments. Among them, the polymerization reaction includes homopolymerization reaction and copolymerization reaction of olefins with polar monomers.

[0177] Example 10

[0178] Method for ethylene homopolymerization: In a glove box, under a nitrogen atmosphere, 18 mL of dichloromethane was added to the pressure-resistant bottle of a 350 mL autoclave (equipped with a magnetic stirring device, an oil bath heating device, and a thermometer). The container was connected to a high-pressure pipeline and the pipeline was evacuated. The container was controlled at an appropriate temperature using a water bath, and a certain amount of the diimine palladium catalyst prepared in the examples dissolved in 2 mL of dichloromethane was injected into the polymerization system through a syringe. The valve was closed, and after adjusting the ethylene pressure to 8 atmospheres, the reaction was carried out for 2 hours. The reaction was stopped, the autoclave was opened, and the resulting polymer was dried under vacuum to obtain a yellow oil. The polymerization results are shown in Table 2.

[0179] Table 2. Influence of palladium compounds on the catalytic ethylene homopolymerization reaction

[0180]

[0181] In Table 2: The polymerization reaction conditions were Pd catalyst = 10 μmol, time = 2 h, dichloromethane (DCM) = 20 mL, ethylene pressure = 8 atm, where the polymerization was repeated at least 2 times or more. b Activity = 10 4 g·mol -1 ·h -1 . c The molecular weight was measured by GPC using tetrahydrofuran as the solvent at 25 °C. d Using 1 1H NMR analysis to determine the degree of branching of polyethylene. In Table 2, Pd corresponds to the compound shown in Formula (III), Pd-Na + represents the reaction of the compound of Formula (III) with NaH, Pd-K + represents the reaction of the compound of Formula (III) with KH; Pd + corresponds to the compound shown in Formula (IV), Pd + -Na + represents the reaction of the compound of Formula (IV) with NaH, Pd + -K + represents the reaction of the compound of Formula (IV) with KH.

[0182] By comparing the data in the first, second, and third rows of Table 2, after adding metal ions, in the ethylene homopolymerization reaction catalyzed by the compound shown in Formula (III), the polymerization activity (Act) of the polymer increased, and the molecular weight of the polymer (M n ) also increased. Thus, it can be seen that the interaction between metal Pd and metal ions makes the β-H elimination less likely to occur during the polymerization process, reducing the chain transfer rate, so the activity increases and the molecular weight of the resulting polymer also increases.

[0183] By comparing the data in the 1st row and the 4th row of Table 2, after adding AgBAF for oxidation, in the homopolymerization of ethylene catalyzed by the compound shown in Formula (III), the polymerization activity (Act) of the polymer decreases, and the molecular weight (M n ) of the polymer also decreases. The main reason is that: the electron-withdrawing effect of the oxidized ferrocene unit is stronger, which reduces the electron cloud density of the palladium metal center, making it electrophilic. In the polymerization process, β-H elimination is more likely to occur, increasing the chain transfer rate. Therefore, the activity decreases, the molecular weight of the obtained polymer decreases, and the degree of branching increases.

[0184] By comparing the data in the 2nd row and the 3rd row, and the 5th row and the 6th row of Table 2, after adding AgBAF for oxidation and then adding metal ions, in the homopolymerization of ethylene catalyzed by the compound shown in Formula (III), the polymerization activity (Act) of the polymer decreases, and the molecular weight (M n ) of the polymer also decreases. Thus, it can be seen that redox regulation plays a dominant role.

[0185] Furthermore, the effects of metal ions with different valence states and palladium catalysts on the homopolymerization of ethylene were investigated, and the specific test results are shown in Table 3.

[0186] Table 3. Effects of Palladium Catalysts and Metal Ions with Different Valence States on the Homopolymerization of Ethylene

[0187]

[0188] In Table 3: The polymerization reaction conditions are Pd catalyst = 10 μmol, time = 2 h, DCM = 20 mL, ethylene pressure = 8 atm, and the number of polymerization repetitions is at least 2 times or more. b Activity = 10 4 g·mol -1 ·h -1 . c The molecular weight was measured by GPC at 25 °C using tetrahydrofuran as the solvent. d Using 1 1H NMR analysis to determine the degree of branching of polyethylene. Among them, Pd-Mg 2+ represents the product of the reaction of the compound shown in Formula (III) with MgCl2, and the synthesis route is shown in Formula (XVI); Pd-Fe 3+ represents the product of the reaction of the compound shown in Formula (III) with FeCl3, and the synthesis route is shown in Formula (XVII); Pd-Ti 4+ represents the product of the reaction of the compound shown in Formula (III) with TiCl4, and the synthesis route is shown in Formula (XVIII); Pd + -Mg 2+ represents the reaction of the compound shown in Formula (IV) with MgCl2, and Pd + -Fe 3+ represents the reaction of the compound shown in Formula (IV) with FeCl3, and Pd+ -Ti 4+ The compound of formula (IV) reacts with TiCl4.

[0189] By comparing the data in the 1st, 3rd, and 5th rows of Table 3, after adding metal ions with different valence states, in the ethylene homopolymerization reaction catalyzed by the compound shown in formula (III), the polymerization activity (Act) of the polymer changes little, but the molecular weight of the polymer (M n ) increases. It can be seen that the metal-metal interaction between higher-valent metals is stronger, resulting in an increase in the molecular weight of the obtained polymer.

[0190] By comparing the data in the 1st and 2nd rows of Table 3, after oxidation with AgBAF, in the ethylene homopolymerization reaction catalyzed by the compound shown in formula (IV), the polymerization activity (Act) of the polymer decreases, and the molecular weight of the polymer (M n ) also decreases. It can be seen that the electron-withdrawing effect of the oxidized ferrocene unit is stronger, reducing the electron cloud density of the palladium metal center and making it more electrophilic. The β-H elimination is more likely to occur during the polymerization process, that is, the chain transfer rate is increased, so the activity decreases and the molecular weight of the obtained polymer decreases.

[0191] Example 11

[0192] In the glove box, under a nitrogen atmosphere, a certain amount of dichloromethane and polar monomer were added to the pressure-resistant bottle of a 350 mL autoclave (equipped with a magnetic stirring device, an oil bath heating device, and a thermometer). The container was connected to the high-pressure pipeline and the pipeline was evacuated. The container was controlled at an appropriate temperature using a water bath, and a certain amount of the palladium catalyst prepared in the example dissolved in 2 mL of dichloromethane was injected into the polymerization system through a syringe. The valve was closed, and after adjusting the ethylene pressure to 8 atmospheres, the reaction was carried out for 2 hours. The reaction was stopped, the autoclave was opened, and the obtained polymer was vacuum-dried to remove the solvent to obtain a yellow oil. The test results of the copolymerization reaction are shown in Table 4 below.

[0193] Table 4. Influence of Palladium Compounds on the Copolymerization Reaction of Ethylene with Different Polar Monomers

[0194]

[0195] In Table 4: The polymerization reaction conditions are Pd catalyst = 10 μmol, time = 2 h, DCM = 20 mL, ethylene pressure = 8 atm, total volume of dichloromethane and polar monomer = 20 mL, time = 2 h. Among them, the polymerization was repeated at least 2 times. b Activity = 10 4 g·mol -1 ·h -1 . c The molecular weight was measured by GPC at 25 °C using tetrahydrofuran as the solvent.d The insertion ratio of the polar monomer was determined by 1 1H NMR. Among them, MUA represents methyl 10-undecenoate, and MA represents methyl acrylate; Pd in Table 3 corresponds to the compound shown in Formula (III); Pd + corresponds to the compound shown in Formula (IV).

[0196] By comparing the data in the first, second, and third rows of Table 4, after adding ions, in the copolymerization reaction of ethylene and polar monomer catalyzed by the compound shown in Formula (III), the polymerization activity (Act) of the polymer increases, and the molecular weight of the polymer (M n ) also increases. Thus, it can be seen that the interaction between Pd metal and metal ions makes it less likely for β-H elimination to occur during the polymerization process, that is, the chain transfer rate is reduced, so the activity increases, and the molecular weight of the obtained polymer also increases.

[0197] By comparing the data in the first and fourth rows of Table 4, after oxidation with AgBAF, in the copolymerization reaction of ethylene and polar monomer catalyzed by the compound shown in Formula (IV), the polymerization activity (Act) of the polymer decreases, and the molecular weight of the polymer (M n ) also decreases. Thus, it can be seen that the electron-withdrawing effect of the oxidized ferrocene unit is stronger, which reduces the electron cloud density of the palladium metal center and makes it more electrophilic. β-H elimination is more likely to occur during the polymerization process, that is, the chain transfer rate is increased, so the activity is reduced, and the molecular weight of the obtained polymer is reduced.

[0198] By comparing the data in the second, third, fifth, and sixth rows of Table 4, after oxidation and then adding ions, in the copolymerization reaction of ethylene and polar monomer catalyzed by the compound shown in Formula (III), the polymerization activity (Act) of the polymer decreases, but the molecular weight of the polymer (M n ) increases. Thus, it can be seen that the regulation of metal ions plays a dominant role.

[0199] The specific embodiments described above have further elaborated on the purpose, technical solutions, and beneficial effects of the present disclosure. It should be understood that the above are only specific embodiments of the present disclosure and are not used to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present disclosure should be included within the protection scope of the present disclosure.

Claims

1. A ligand compound with a metal ion regulation effect, characterized in that, It has the structure shown in formula (I): Formula (I) Wherein, Ar1 is selected from substituted phenyl groups, and the substituted phenyl groups carry at least one ferrocene substituent; Ar2 is selected from substituted naphthyl groups, and the substituted naphthyl groups carry at least one phenyl group substituted with a carboxyl group.

2. The ligand compound according to claim 1, characterized in that: The substituted phenyl group also carries at least one substituent selected from benzhydryl, isopropyl, methyl, tert-butyl, and phenyl; and / or The substituted naphthyl group also carries at least one substituent selected from isopropyl, methyl, tert-butyl, and phenyl.

3. A method for preparing the ligand compound according to claim 1, characterized in that, The method includes: React compound A with compound B to obtain compound C , and then react with compound D to obtain the ligand compound having the structure shown in formula (I); Wherein, Ar1 is selected from substituted phenyl groups, and the substituted phenyl groups carry at least one ferrocene substituent; Ar2 is selected from substituted naphthyl groups, and the substituted naphthyl groups carry at least one phenyl group substituted with a carboxyl group.

4. The method according to claim 3, characterized in that: Adding compound B and an organic acid catalyst to an organic solution of compound A, reacting at a preset temperature to obtain compound C; Adding the compound C and the organic acid catalyst to an organic solution of compound D, reacting at the preset temperature to obtain a ligand compound having the structure shown in formula (I), Wherein: The solvent of the organic solution is selected from: methanol; The organic acid catalyst is selected from any one of formic acid and acetic acid; The preset temperature is 25°C - 80°C, and the reaction time is 24h - 48h; The molar ratio of compound B to compound A is 3 - 5:1, and the molar ratio of compound D to compound C is 1 - 2:

1.

5. A palladium compound, characterized in that, It has the structure shown in formula (II): Formula (II); Wherein, Ar1 is selected from substituted phenyl groups, and the substituted phenyl groups carry at least one ferrocene substituent; Ar2 is selected from substituted naphthyl groups, and the substituted naphthyl groups carry at least one phenyl group substituted with a carboxyl group.

6. A method for preparing the palladium compound according to claim 5, characterized in that, The method includes: Adding a metal palladium precursor to an organic solution of the ligand compound having the structure shown in formula (I) of claim 1, reacting to obtain a palladium compound having the structure shown in formula (II); Wherein: The solvent of the organic solution is dichloromethane; The metal palladium precursor is chloro(1,5-cyclooctadiene)methylpalladium; The molar ratio of the ligand compound to the metal palladium precursor is 1:1 - 1:1.2; The reaction time is 12 - 24h.

7. A diimine palladium catalyst, characterized in that, A palladium cation compound having the structure shown in formula (III): Formula (III); Or an oxide having the structure shown in formula (IV): Formula (IV); Wherein, Ar1 is selected from substituted phenyl groups, and the substituted phenyl groups carry at least one ferrocene substituent; Ar2 is selected from substituted naphthyl groups, said substituted naphthyl groups bearing at least one carboxyl-substituted phenyl group, represents a tetrakis(3,5-bis(trifluoromethyl)phenyl)borate anion.

8. A method for preparing the diimine palladium catalyst according to claim 7, characterized in that, The method includes: Reacting the palladium compound having the structure shown in formula (II) of claim 5 with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate in an acetonitrile solution to obtain the palladium cation compound having the structure shown in formula (III); or Reacting the palladium cation compound having the structure shown in formula (III) with silver tetrakis(3,5-bis(trifluoromethyl)phenyl)borate to obtain the oxide having the structure shown in formula (IV).

9. A diimine catalyst having a metal ion regulating effect, characterized in that, The diimine catalyst is selected from: The palladium cation compound having the structure shown in formula (III) of claim 7 and a metal cation combined with a carboxyl group; or; The oxide shown in formula (IV) as claimed in claim 7 and a metal cation combined with a carboxyl group; The metal cation is Na + , K + , Mg 2+ , Fe 3+ , Ti 4+ or any one of them; Among them, the diimine catalyst with metal ion regulating effect is obtained by reacting a palladium cation compound with the structure shown in the formula (III) or an oxide with the structure shown in the formula (IV) with a metal salt; The metal cation in the metal salt is Na + , K + , Mg 2+ , Fe 3+ or Ti 4+ .

10. A method for preparing polyolefins, characterized in that, The method includes: Under optional preset conditions, using the diimine palladium catalyst according to claim 7 or the diimine catalyst with metal ion regulating effect according to claim 9 to catalyze the homopolymerization reaction of olefins; or Using the diimine palladium catalyst according to claim 7 or the diimine catalyst with metal ion regulating effect according to claim 9 to catalyze the copolymerization reaction of olefins and polar monomers; Among them, the optional preset conditions are selected from at least one of the following: Ultraviolet, visible light irradiation, using a Lewis acid additive.

11. The method according to claim 10, characterized in that: The Lewis acid additive is selected from tris(pentafluorophenyl)borane; The olefin is selected from: ethylene or propylene; The polar monomer is selected from: methyl acrylate, methyl 10-undecenoate, norbornene; The reaction temperature is 0°C - 60°C.

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