Macromolecular alpha-diimine nickel, palladium catalysts, methods for their preparation and use

Abstract

The application provides a macromolecular alpha-diimine nickel and palladium catalyst, and a preparation method and application thereof.The macromolecular alpha-diimine nickel and palladium catalyst provided by the application has a structure shown in formula I or II, contains a double bond on a skeleton, and is special in structure; when the catalyst is used to catalyze ethylene polymerization, it is found that the catalytic activity is high, and can reach 2.5*10 7 g mol ‑1 h ‑1 Above; and the molecular weight and the branching degree of the prepared polymer can be greatly adjusted, and branched polyolefin with a molecular weight of 0.3-38.0*103 and a branching degree of 48-111 / 1000C can be prepared.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of olefin catalysis, and particularly relates to a macromolecular alpha-diimine nickel and palladium catalyst, a preparation method and application thereof. BACKGROUND

[0002] Since 1995, due to the unique chain walking mechanism, the alpha-diimine post-transition metal nickel and palladium catalyst has been widely concerned by the academic and industrial circles. It is reported in the literature (J. Am. Chem. Soc. 1995, 117, 6414) that the alpha-diimine nickel and palladium catalyst has now become a very useful ethylene polymerization catalyst, which can prepare branched polyolefins with ethylene as the only monomer. However, it is pointed out in the literature (Eur. Polym. J. 2022, 181, 111693) that there are still some problems to be solved in this catalytic system, such as the low activity of the catalyst at high temperature, which cannot be applied to industrial production, etc.

[0003] In order to solve these problems, the common method at present is to modify the ligand structure of the catalyst, and adjust the electronic effect and steric effect of the ligand to improve the thermal stability of the catalyst. However, although the spatial effect and electronic effect of the ligand can be adjusted to obtain high-branched polymers, the polymerization activity is generally not high, and it is difficult to efficiently prepare polyolefin elastomers. In addition, the catalyst has poor heat resistance, especially at temperatures above 70℃, and has low molecular weight and low activity. These two points limit the application of the alpha-diimine nickel and palladium catalyst to some extent. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a macromolecular alpha-diimine nickel and palladium catalyst, a preparation method and application thereof. The catalyst has high catalytic activity, and the molecular weight and branching degree of the prepared polymer can be greatly adjusted.

[0005] To achieve this purpose, the technical scheme adopted by the present application is as follows:

[0006] In a first aspect, the present application provides a macromolecular alpha-diimine nickel and palladium catalyst, which has the structure shown in formula I or II:

[0007] Formula I; Formula II;

[0008] wherein R 1 , R 2 , R 4 and R 5 are each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl;

[0009] R3 and R 6 each independently selected from hydrogen, hydroxyl, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy;

[0010] M is nickel or palladium;

[0011] X is halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl;

[0012] n is 2-1000.

[0013] Preferably, the R 1 , R 2 , R 4 and R 5 each independently selected from substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C6-C20 aryl.

[0014] Preferably, R 3 and R 6 each independently selected from hydrogen, hydroxyl, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy.

[0015] Preferably, X is halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C6-C20 aryl.

[0016] More preferably, the R 1 , R 2 , R 4 and R 5 each independently selected from methyl, phenyl, isopropyl or benzhydryl.

[0017] More preferably, R 3 and R 6 each independently selected from hydrogen, methyl, hydroxyl, halogen or methoxy.

[0018] More preferably, X is halogen, substituted or unsubstituted C1-C3 alkyl, substituted or unsubstituted C6-C18 aryl.

[0019] Further preferably, the macromolecular nickel, palladium α-diimine catalyst is selected from any one of the following formulae:

[0020] .

[0021] In a second aspect, the present application also provides a preparation method of the macromolecular nickel, palladium α-diimine catalyst having the structure shown in the formula I or formula II, comprising:

[0022] S1-1: mixing and reacting norbornenedione or cyclooctenedione with substituted arylamine shown in formula A respectively to obtain compound shown in formula L1 or formula L2;

[0023] S2-1: mixing and reacting compound shown in formula L1 or formula L2 with nickel source or palladium source respectively to obtain compound shown in formula C1 or formula C2;

[0024] S3-1: polymerizing compound shown in formula C1 or formula C2 in the presence of catalyst to obtain macromolecular α-diimine nickel, palladium catalyst shown in formula I or formula II;

[0025] Formula A; Formula L1; Formula C1; Formula L2; Formula C2;

[0026] or

[0027] S1-2: obtaining compound shown in formula L1 or formula L2 according to the method of S1-1;

[0028] S2-2: polymerizing compound shown in formula L1 or formula L2 in the presence of catalyst to obtain compound shown in formula L1-P or L2-P respectively;

[0029] S3-2: mixing and reacting compound shown in formula L1-P or L2-P with nickel source or palladium source to obtain macromolecular α-diimine nickel, palladium catalyst shown in formula I or formula II respectively;

[0030] Formula L1-P; Formula L2-P.

[0031] Preferably, the molar ratio of norbornenedione or cyclooctenedione to substituted arylamine shown in formula A is 1:1-1:20.

[0032] Preferably, the molar ratio of compound shown in formula L1 or formula L2 to nickel source or palladium source is 1:1-1:10.

[0033] Preferably, the molar ratio of compound shown in formula C1 or formula C2 to catalyst is 10:1-1000:1.

[0034] Preferably, the molar ratio of compound shown in formula L1 or formula L2 to catalyst is 10:1-1000:1.

[0035] Preferably, the molar ratio of compound shown in formula L1-P or formula L2-P to nickel source or palladium source is 1:n.

[0036] Preferably, the temperature of the reaction in step S1-1 is 20-80℃, and the time of the reaction is 2-10 h.

[0037] Preferably, the temperature of the reaction in step S2-1 or step S3-2 is independently 15-30℃, and the time of the reaction is independently 40-90 h.

[0038] Preferably, the temperature of the polymerization in step S2-2 or step S3-1 is independently 15-30℃, and the time of the polymerization is independently 5-20 h.

[0039] Preferably, the nickel source is selected from ethylene glycol dimethyl ether nickel bromide and / or ethylene glycol dimethyl ether nickel chloride.

[0040] Preferably, the palladium source is selected from chloro(1,5-cyclooctadiene)methyl palladium(II).

[0041] Preferably, the catalyst is selected from any one or more of Grubbs I catalyst, Grubbs II catalyst, Grubbs III catalyst, Hoveyda-Grubbs I catalyst or Hoveyda-Grubbs II catalyst.

[0042] In a third aspect, the present application provides an application of the above-mentioned macromolecular α-diimine nickel, palladium catalyst in ethylene polymerization.

[0043] Preferably, in the above-mentioned application, the application temperature of the macromolecular α-diimine nickel, palladium catalyst is ≥0℃.

[0044] Compared with the prior art, the present application has the following beneficial effects:

[0045] Based on the norbornene diketone and cyclooctene diketone skeleton containing cyclic double bond, the present application develops a new type of macromolecular α-diimine nickel, palladium catalyst, which can be simply converted from mononuclear catalyst to macromolecular multi-nuclear catalyst through ring-opening allograph polymerization, avoiding the side reaction of double-molecule deactivation in small molecule catalyst system, and improving the catalytic activity and thermal stability in ethylene polymerization.

[0046] Tests show that the macromolecular α-diimine nickel, palladium catalyst provided by the present application has high catalytic activity, which can reach 2.5×10 7 g mol -1 h -1 The above; and the molecular weight and branching degree of the polymer prepared by using it as a catalyst to catalyze ethylene polymerization can be greatly adjusted, and branched polyolefin with a molecular weight of 0.3-380,000 and a branching degree of 48-111 / 1000C can be prepared. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 The single crystal diffraction pattern of the alpha-diimine nickel complex Ni3 in Example 7;

[0048] Figure 2 The hydrogen spectrum of the polymer prepared corresponding to No. 11 in Table 3;

[0049] Figure 3 The stress-strain curve of the polymer prepared corresponding to No. 5, 9 and 10 in Table 3;

[0050] Figure 4 The elastic recovery curve of the polymer prepared corresponding to No. 5 in Table 3. DETAILED DESCRIPTION

[0051] The technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0052] At present, although the space effect and electronic effect of the ligand can be regulated to obtain highly branched polymers in the catalysis of ethylene polymerization by the alpha-diimine nickel and palladium catalysts, the polymerization activity is generally not high, and it is difficult to efficiently prepare polyolefin elastomers. In addition, the alpha-diimine nickel and palladium catalysts have poor heat resistance, especially at above 70℃, and have low molecular weight and low activity, which to some extent limits the application of the alpha-diimine nickel and palladium catalysts.

[0053] Based on this, the present application innovatively proposes the concept of “macromolecular catalyst”, and develops a new type of macromolecular alpha-diimine nickel and palladium catalyst based on the norbornene diketone and cyclooctene diketone skeleton containing cyclic double bonds. Through ring-opening metathesis polymerization, the mononuclear catalyst can be simply converted into a macromolecular multi-nuclear catalyst, thereby improving the catalytic activity and thermal stability thereof in ethylene polymerization.

[0054] In the present application, the macromolecular alpha-diimine nickel and palladium catalyst has the structure shown in Formula I or II:

[0055] Formula I; Formula II;

[0056] wherein R 1 , R 2 , R 4 and R 5 are each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl;

[0057] R3 and R 6 each independently is selected from the group consisting of hydrogen, hydroxyl, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy;

[0058] M is nickel or palladium;

[0059] X is halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C30 aryl;

[0060] n is 2-1000, specifically 2, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000, etc.

[0061] The above point values are merely for enumeration, and the specific value of n is not limited thereto, and other point values within the value range thereof can also be applicable, and for the sake of brevity, will not be repeated here.

[0062] In some embodiments of the present application, the macromolecular α-diimine nickel, palladium catalyst has the structure shown in Formula I or II. Wherein, R 1 , R 2 , R 4 and R 5 each independently is preferably selected from the group consisting of substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C6-C20 aryl; R 3 and R 6 each independently is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy; X is preferably halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C6-C20 aryl.

[0063] In some embodiments of the present application, the macromolecular α-diimine nickel, palladium catalyst has the structure shown in Formula I or II. Wherein, R 1 , R 2 , R 4 and R 5 each independently is selected from the group consisting of methyl, phenyl, isopropyl or benzhydryl; R 3 and R 6 each independently is selected from the group consisting of hydrogen, methyl, hydroxyl, halogen or methoxy; X is further preferably halogen, substituted or unsubstituted C1-C3 alkyl, substituted or unsubstituted C6-C18 aryl.

[0064] In the present application, in the above "substituted or unsubstituted", the "substituted" group can be selected from C1-C3 alkyl or C6-C18 aryl.

[0065] In some embodiments of the present application, the macromolecular α-diimine nickel, palladium catalyst is selected from any one of the following formulas:

[0066] .

[0067] It should be noted that in the present application, R 1 , R 2 , R 3 , R 4 and R 5 and R 6 are groups connected on the benzene ring, which can be the same or different groups from each other.

[0068] The present application also provides a preparation method of the macromolecular α-diimine nickel, palladium catalyst described above. In the present application, the preparation method of the macromolecular α-diimine nickel, palladium catalyst having the structure shown in Formula I has two synthetic routes: Route 1 and Route 2.

[0069] In Route 1, the preparation method mainly includes the following steps:

[0070] S1-1: mixing and reacting norbornene dione with a substituted arylamine shown in Formula A to obtain a compound shown in Formula L1;

[0071] S2-1: mixing and reacting the compound shown in Formula L1 with a nickel source or a palladium source to obtain a compound shown in Formula C1;

[0072] S3-1: polymerizing the compound shown in Formula C1 in the presence of a catalyst to obtain the macromolecular α-diimine nickel, palladium catalyst having the structure shown in Formula I;

[0073] Formula A; Formula L1; Formula C1.

[0074] In the present application, first, norbornene dione is mixed and reacted with substituted arylamine shown in formula A to obtain compound shown in formula L1. Among them, the molar ratio of norbornene dione to substituted arylamine shown in formula A is 1:1-1:20, preferably 1:2-1:5, more preferably 1:2. The reaction temperature is 20-80℃, preferably 30-60℃, and the reaction time is 2-10 h, preferably 3-8 h. In some embodiments of the present application, preferably, 1 equivalent of norbornene dione, N equivalent of substituted arylamine, and 1:N (N≥2, the larger N, the shorter the reaction time) equivalent of raw materials are fed into a mixture of methanol and formic acid, and reacted at 20-80℃ for more than 6 hours to obtain the compound shown in formula L1. In some preferred embodiments of the present application, after the reaction is completed, it is also preferred to perform post-treatment, that is, the product is precipitated after the reaction solution is cooled (-78℃-0℃), the solid is separated by filtration, washed with cold methanol (or cold ethanol) three times, and dried under vacuum to obtain the compound shown in formula L1 (also known as “α-diimine ligand”) with a yield of more than 10%.

[0075] Then, the compound shown in formula L1 is mixed and reacted with a nickel source or a palladium source to obtain a compound shown in formula C1. In the present application, the molar ratio of the compound shown in formula L1 to the nickel source or the palladium source is 1:1-1:10, preferably 1:1-1:5, more preferably 1:1-1:2; the nickel source is selected from ethylene glycol dimethyl ether nickel bromide; and the palladium source is selected from chloro(1,5-cyclooctadiene)methyl palladium(II). The reaction temperature is 15-30℃, preferably 20-25℃; and the reaction time is 40-90 h, preferably 48-72 h. In some embodiments of the present application, 1 equivalent of α-diimine ligand (formula L1) and 1 equivalent of nickel source or palladium source are fed, stirred in a mixture of dichloromethane at 25℃ for 72 hours. After the reaction is completed, filtration is performed, and the solvent is extracted to obtain the compound shown in formula C1 with a yield of more than 90%.

[0076] Then, according to the present application, the compound shown in formula C1 is polymerized in the presence of a catalyst to obtain a macromolecular α-diimine nickel, palladium catalyst shown in formula I. The catalyst is used to catalyze the polymerization of the compound shown in formula C1 itself, and can be selected from Grubbs II catalyst. The polymerization temperature is 15-30℃, preferably 20-25℃; and the reaction time is 5-20 h, preferably 6-12 h. In some embodiments of the present application, the compound shown in formula C1 is dissolved in dichloromethane to prepare a 0.01-0.1 M solution, and a catalytic amount of Grubbs II catalyst is added, and stirred at room temperature for 12 h. After the reaction is completed, the solution is poured into 40 mL of hexane, and after filtration and drying, the macromolecular α-diimine nickel, palladium catalyst shown in formula I is obtained with a yield of more than 95%.

[0077] In the present application, the route 2 for synthesizing the macromolecular α-diimine nickel, palladium catalyst represented by formula I mainly comprises the following steps:

[0078] S1-2: mixing and reacting norbornadiene with the substituted arylamine represented by formula A to obtain the α-diimine ligand represented by formula L1;

[0079] S2-2: polymerizing the compound represented by formula L1 in the presence of a catalyst to obtain the compound represented by formula L1-P;

[0080] S3-2: mixing and reacting the compound represented by formula L1-P with a nickel source or a palladium source to obtain the macromolecular α-diimine nickel, palladium catalyst represented by formula I;

[0081] Formula A; Formula L1; Formula L1-P.

[0082] In the present application, the scheme for obtaining the compound represented by formula L1 is described above in the relevant content of route 1, which is not repeated here.

[0083] According to the present application, after obtaining the compound represented by formula L1, route 2 first polymerizes it in the presence of a catalyst to obtain the compound represented by formula L1-P. The molar ratio of the compound represented by formula L1 to the catalyst is 10:1 to 1000:1, preferably 20:1 to 800:1, and more preferably 50:1 to 300:1. The catalyst is used to catalyze the polymerization of the compound represented by formula L1 itself, and can be specifically selected from Grubbs II catalyst. The temperature of the polymerization is 15 to 30°C, preferably 20 to 25°C; and the reaction time is 5 to 20 h, preferably 6 to 12 h. In some embodiments of the present application, the α-diimine ligand (formula L1) is preferably dissolved in dichloromethane to prepare a 0.01 to 0.1 M solution, and a catalytic amount of Grubbs II catalyst is added, and stirred at room temperature for 6 hours. After the reaction is completed, the solution is poured into 40 mL of hexane, and L1-P is obtained after filtration and drying, with a yield of more than 95%.

[0084] Then, the compound shown as formula L1-P is mixed with a nickel source or a palladium source and reacted to obtain the macromolecular α-diimine nickel, palladium catalyst shown as formula I. The molar ratio of the compound shown as formula L1-P to the nickel source or the palladium source is 1: n. The selection of the nickel source or the palladium source is as described above in the related content of the technical solutions, which is not repeated here. The temperature of the reaction is 15-30°C, preferably 20-25°C; the time of the reaction is 40-90 h, preferably 48-72 h. In some embodiments of the present application, 1 equivalent of the compound shown as formula L1-P and 1 equivalent of the nickel source or the palladium source (relative to the polymerization unit in L1-P) are fed into a mixed solution of dichloromethane, stirred at 25°C for 72 hours. After the reaction is completed, filtration is performed, and the solvent is dried to obtain the macromolecular α-diimine nickel, palladium catalyst shown as formula I.

[0085] The present application also provides a preparation method of a macromolecular α-diimine nickel, palladium catalyst having a structure shown as formula II, which also includes two routes of route 1 and route 2.

[0086] Among them, route 1 mainly includes:

[0087] S1-1: mixing and reacting cyclooctenedione with the substituted arylamine shown as formula A to obtain the compound shown as formula L2;

[0088] S2-1: mixing and reacting the compound shown as formula L2 with a nickel source or a palladium source to obtain the compound shown as formula C2;

[0089] S3-1: polymerizing the compound shown as formula C2 under the action of a catalyst to obtain the macromolecular α-diimine nickel, palladium catalyst having a structure shown as formula III;

[0090] Formula A; Formula L2; Formula C2;

[0091] In the present application, the cyclooctenedione is first mixed and reacted with the substituted aniline of formula A to obtain the compound of formula L2. The molar ratio of the cyclooctenedione to the substituted aniline of formula A is 1:1-1:20, preferably 1:2-1:5, and more preferably 1:2. The reaction temperature is 20-80°C, preferably 30-60°C, and the reaction time is 2-10 h, preferably 3-8 h. In some embodiments of the present application, preferably, 1 equivalent of cyclooctenedione and N equivalents of substituted aniline are fed in a 1:N (N≥2, the larger N is, the shorter the reaction time is) equivalent ratio, and the mixture is reacted in a mixed solution of methanol and formic acid at 20-80°C for more than 6 h to obtain the compound of formula L2. In some preferred embodiments of the present application, after the reaction is completed, the product is preferably precipitated after the reaction solution is cooled (-78°C-0°C), and the solid is separated by filtration, washed with cold methanol (or cold ethanol) three times, and dried under vacuum to obtain the compound of formula L2 with a yield of more than 10%.

[0092] Then, the compound of formula L2 is mixed and reacted with a nickel source or a palladium source to obtain the compound of formula C2. In the present application, the molar ratio of the compound of formula L2 to the nickel source or the palladium source is 1:1-1:10, preferably 1:1-1:5, and more preferably 1:1-1:2. The nickel source is selected from the group consisting of ethylene glycol dimethyl ether nickel bromide and / or ethylene glycol dimethyl ether nickel chloride; and the palladium source is selected from chloro(1,5-cyclooctadiene)methyl palladium(II). The reaction temperature is 15-30°C, preferably 20-25°C, and the reaction time is 40-90 h, preferably 48-72 h. In some embodiments of the present application, 1 equivalent of the compound of formula L2 and 1 equivalent of the nickel source or the palladium source are fed, and the mixture is stirred in a mixed solution of dichloromethane at 25°C for 72 h. After the reaction is completed, the product is filtered and the solvent is removed by suction to obtain the compound of formula C2 with a yield of more than 90%.

[0093] Then, according to the present application, the compound shown in formula C2 is polymerized under the action of a catalyst to obtain a macromolecular α-diimine nickel, palladium catalyst shown in formula I. The catalyst is used to catalyze the polymerization of the compound shown in formula C1 itself, and can be selected from any one or more of Grubbs I catalyst, Grubbs II catalyst, Grubbs III catalyst, Hoveyda-Grubbs I catalyst or Hoveyda-Grubbs II catalyst. The temperature of the polymerization is 15-30°C, preferably 20-25°C; the reaction time is 5-20 h, preferably 6-12 h. In some embodiments of the present application, the compound shown in formula C2 is dissolved in dichloromethane to prepare a 0.01-0.1 M solution, and a catalytic amount of Grubbs II catalyst is added, and stirred at room temperature for 12 hours. After the reaction is completed, the solution is poured into 40 mL of hexane, and after filtration and drying, a macromolecular α-diimine nickel, palladium catalyst shown in formula II is obtained, with a yield of more than 95%.

[0094] In the present application, route 2 for synthesizing the macromolecular α-diimine nickel, palladium catalyst shown in formula II according to the present application mainly includes the following steps:

[0095] S1-2: mixing and reacting cyclooctenedione with the substituted arylamine shown in formula A to obtain the α-diimine ligand shown in formula L2;

[0096] S2-2: polymerizing the compound shown in formula L2 under the action of a catalyst to obtain the compound shown in formula L2-P;

[0097] S3-2: mixing and reacting the compound shown in formula L2-P with a nickel source or a palladium source to obtain the macromolecular α-diimine nickel, palladium catalyst shown in formula II;

[0098] Formula A; Formula L2; Formula L2-P.

[0099] In the present application, the scheme for obtaining the compound shown in formula L2 is described above in the relevant content of route 1, which is not repeated here.

[0100] According to the present application, after obtaining the compound shown in formula L1, the compound shown in formula L2 is first polymerized under the action of a catalyst to obtain the compound shown in formula L2-P. The molar ratio of the compound shown in formula L2 to the catalyst is 10:1-1000:1, preferably 20:1-800:1, and more preferably 50:1-300:1. The catalyst is used to catalyze the polymerization of the compound shown in formula L2 itself, and can be specifically selected from any one or more of Grubbs I catalyst, Grubbs II catalyst, Grubbs III catalyst, Hoveyda-Grubbs I catalyst, or Hoveyda-Grubbs II catalyst. The temperature of the polymerization is 15-30°C, preferably 20-25°C; and the reaction time is 5-20 h, preferably 6-12 h. In some embodiments of the present application, the compound shown in formula L2 is preferably dissolved in dichloromethane to prepare a 0.01-0.1 M solution, and a catalytic amount of Grubbs II catalyst is added, and stirred at room temperature for 6 hours. After the reaction is completed, the solution is poured into 40 mL of hexane, and after filtration and drying, the compound shown in formula L2-P is obtained, with a yield of more than 95%.

[0101] Then, the compound shown in formula L2-P is mixed with a nickel source or a palladium source and reacted to obtain the macromolecular nickel, palladium catalyst of α-diaimine shown in formula II. The molar ratio of the compound shown in formula L2-P to the nickel source or the palladium source is 1:n. The selection of the nickel source or the palladium source is as described above in the related content of the technical solutions, and will not be repeated here. The reaction temperature is 15-30°C, preferably 20-25°C; and the reaction time is 40-90 h, preferably 48-72 h. In some embodiments of the present application, preferably, 1 equivalent of the nickel source or the palladium source (relative to the polymerization unit in L2-P) is added according to 1 equivalent of formula L2-P, and stirred in a mixed dichloromethane solution at 25°C for 72 hours. After the reaction is completed, filtration is performed, and the solvent is dried to obtain the macromolecular nickel, palladium catalyst of α-diaimine shown in formula II, with a yield of more than 90%.

[0102] In the present application, the synthesis route of the macromolecular nickel, palladium catalyst of α-diaimine shown in formula I or II is as follows:

[0103] .

[0104] In some embodiments of the present application, monomeric α-diimine nickel catalyst and macromolecular α-diimine nickel catalysts with different polymerization degrees are used as catalysts for ethylene polymerization. It is found that with the increase of the polymerization degree of the macromolecular α-diimine nickel catalyst, the activity of the catalyst for ethylene homopolymerization increases greatly, and the molecular weight of the polymer increases significantly. In addition, for the same catalyst, with the increase of the temperature, the activity of the catalyst decreases, the molecular weight of the polymer decreases, and the branching degree of the polymer increases. The monomeric α-diimine nickel catalyst loses activity at 90℃, but the macromolecular α-diimine nickel catalyst still has high activity at 90℃.

[0105] Similarly, in some other embodiments of the present application, monomeric α-diimine palladium catalyst and macromolecular α-diimine palladium catalysts with different polymerization degrees are used as catalysts for ethylene polymerization. It is found that under the same conditions, the macromolecular α-diimine palladium catalyst has higher polymerization activity than the monomeric α-diimine palladium catalyst, the molecular weight of the polymer prepared is higher, the branching degree of the polymer is lower, and the molecular weight distribution of the polymer is narrower.

[0106] In addition, in some embodiments of the present application, scale-up experiments of the monomeric α-diimine nickel catalyst and the macromolecular α-diimine nickel catalyst represented by formula I are also carried out. It is found that under the scale-up conditions, the macromolecular α-diimine nickel catalyst can still be used to prepare high-branched polyethylene elastomers with high activity, and the highest activity is 12×10 6 g mol -1 h -1 , i.e. 18 kg PE / g Cat . In comparison, the monomeric α-diimine nickel catalyst has lower activity and molecular weight.

[0107] In summary, the macromolecular α-diimine nickel and palladium catalysts represented by formula I or II provided by the present application have high catalytic activity, and the molecular weight and branching degree of the polymers prepared can be adjusted greatly. Based on this, the present application also provides an application of the macromolecular α-diimine nickel and palladium catalysts in ethylene polymerization.

[0108] In order to further illustrate the present application, the following examples are used to illustrate the present application in detail. The experimental materials used in the following examples of the present application are all commercially available.

[0109] Example 1

[0110] In this embodiment, an α-diimine ligand L1-1 is provided, in which R1, R2, R4 and R5 are methyl, and R3 and R6 are hydrogen.

[0111]

[0112] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,6-dimethylaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5100 g, 60% yield). Example 2

[0113] This example provides an α-diimine nickel complex Ni1, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen; X is bromide;

[0114]

[0115] A mixture of α-diimine ligand L1-1 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni1. (0.24 g, 90% yield).

[0116] Example 3

[0117] This example provides an α-diimine nickel complex Ni2, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen; X is bromide;

[0118]

[0119] A mixture of catalyst Ni1 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, which was Ni2, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0120] Example 4

[0121] This example provides an α-diimine palladium complex Pd1, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen;

[0122]

[0123] A mixture of a-diimine ligand L1-1 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Pd1. (0.24 g, 90% yield).

[0124] Example 5

[0125] This example provides a kind of α-diimine palladium complex Pd2, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen;

[0126]

[0127] A mixture of catalyst Pd1 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, which was Pd2. (188 mg, 94% yield). The catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 39.

[0128] Example 6

[0129] This example provides a kind of α-diimine ligand L1-2, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;

[0130]

[0131] The preparation method is as follows:

[0132] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,6-diisopropylaniline (0.8283 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.1164 g, yield 11%).

[0133] Example 7

[0134] This example provides a kind of α-diimine nickel complex Ni3, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;X is bromine;

[0135]

[0136] A mixture of α-diimine ligand L1-2 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, namely Ni3. (0.24 g, 90 % yield).

[0137] The single crystal diffraction pattern of Ni3 is shown in Figure 1

[0138] Example 8

[0139] This example provides an α-diimine nickel complex Ni4, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen; X is bromine;

[0140]

[0141] A mixture of catalyst Ni3 (0.2 g, 0.30 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 5 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 20 mL hexane, and a brick red solid was obtained after filtration and drying, namely Ni4. (196 mg, 98 % yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 5.

[0142] Example 9

[0143] This example provides an α-diimine nickel complex Ni5, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen; X is bromine;

[0144]

[0145] A mixture of catalyst Ni3 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, namely Ni5. (188 mg, 94 % yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0146] Example 10

[0147] This example provides an α-diimine palladium complex Pd3, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;

[0148]

[0149] ​A mixture of α-diimine ligand L1-2 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd3. (0.24 g, 90 % yield).

[0150] Example 11

[0151] This example provides an α-diimine palladium complex Pd4, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;

[0152]

[0153] A mixture of catalyst Pd3 (0.2 g, 0.30 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 5 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 20 mL hexane, and a brick red solid, Pd4, was obtained after filtration and drying. (196 mg, 98 % yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 11.

[0154] Example 12

[0155] This example provides an α-diimine palladium complex Pd5, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;

[0156]

[0157] A mixture of catalyst Pd3 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Pd5, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 19.

[0158] Example 13

[0159] This example provides an α-diimine ligand L1-3, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl;

[0160]

[0161] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,6-dimethyl-4-hydroxy- aniline (0.6317 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile material was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and dried (0.5227 g, 57% yield).

[0162] Example 14

[0163] This example provides an alpha-diimine nickel complex Ni6, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen; X is bromide;

[0164]

[0165] A mixture of alpha-diimine ligand L1-3 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni6. (0.24 g, 90% yield)

[0166] Example 15

[0167] This example provides an alpha-diimine nickel complex Ni7, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen; X is bromide;

[0168]

[0169] A mixture of catalyst Ni6 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, which was Ni7, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0170] Example 16

[0171] This example provides an alpha-diimine palladium complex Pd6, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl;

[0172]

[0173] A mixture of α-diimine ligand L1-3 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd6. (0.24 g, 90 % yield).

[0174] Example 17

[0175] This example provides an α-diimine palladium complex Pd7, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl;

[0176]

[0177] A mixture of catalyst Pd6 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Pd7, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0178] Example 18

[0179] This example provides an α-diimine ligand L1-4, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen;

[0180]

[0181] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,6-diphenylphenylamine (1.1462 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.9300 g, yield 65 %).

[0182] Example 19

[0183] This example provides an α-diimine nickel complex Ni8, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen; X is bromine;

[0184]

[0185] A mixture of α-diimine ligand L1-4 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Ni8. (0.24 g, 90 % yield).

[0186] Example 20

[0187] This example provides an α-diimine nickel complex Ni9, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen; X is bromine;

[0188]

[0189] A mixture of catalyst Ni8 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, i.e. Ni9. (188 mg, 94 % yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0190] Example 21

[0191] This example provides an α-diimine palladium complex Pd8, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen;

[0192]

[0193] A mixture of α-diimine ligand L1-4 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd8. (0.24 g, 90 % yield).

[0194] Example 22

[0195] This example provides an α-diimine palladium complex Pd9, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen;

[0196]

[0197] A mixture of catalyst Pd8 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL of dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL of hexane, and a red-brown solid, Pd9, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst with a polymerization degree n of 39.

[0198] Example 23

[0199] This example provides an α-diimine ligand L1-5, R1, R2, R4 and R5 are benzhydryl, R3 and R6 are methyl;

[0200]

[0201] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 4-methyl-2,6- diphenylmethylaniline (0.8283 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile material was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and oven dried (0.1164 g, 11% yield).

[0202] Example 24

[0203] This example provides an α-diimine nickel complex Ni10, R1, R2, R4 and R5 are benzhydryl, R3 and R6 are methyl; X is bromide;

[0204]

[0205] A mixture of α-diimine ligand L1-5 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL of dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Ni10. (0.24 g, 90% yield).

[0206] Example 25

[0207] This example provides an α-diimine nickel complex Ni11, R1, R2, R4 and R5 are benzhydryl, R3 and R6 are methyl; X is bromide;

[0208]

[0209] A mixture of catalyst Ni10 (0.2 g, 0.30 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 5 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 20 mL hexane, and a brick red solid was obtained after filtration and drying, which was Ni11. (196 mg, 98% yield). The catalyst was a macromolecular nickel catalyst, and the polymerization degree n was 5.

[0210] Example 26

[0211] This example provides an α-diimine palladium complex Pd10, R1, R2, R4 and R5 are benzhydryl, and R3 and R6 are methyl;

[0212]

[0213] A mixture of α-diimine ligand L1-5 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25°C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Pd10. (0.24 g, 90% yield).

[0214] Example 27

[0215] This example provides an α-diimine palladium complex Pd11, R1, R2, R4 and R5 are benzhydryl, and R3 and R6 are methyl;

[0216]

[0217] A mixture of catalyst Pd10 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, which was Pd11. (188 mg, 94% yield). The catalyst was a macromolecular palladium catalyst, and the polymerization degree n was 39.

[0218] Example 28

[0219] This example provides an α-diimine ligand L1-6, R1, R2, R3, R4, R5 and R6 are methyl;

[0220]

[0221] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,4,6-trimethylaniline (1.1462 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.9300 g, 65% yield).

[0222] Example 29

[0223] This example provides an α-diimine nickel complex Ni12, R1, R2, R3, R4, R5, and R6 are methyl; X is bromide;

[0224]

[0225] A mixture of α-diimine ligand L1-6 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni23. (0.24 g, 90 % yield).

[0226] Example 30

[0227] This example provides an α-diimine nickel complex Ni13, R1, R2, R3, R4, R5, and R6 are methyl; X is bromide;

[0228]

[0229] A mixture of catalyst Ni12 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, which was Ni13, was obtained after filtration and drying. (190 mg, 94% yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 12.

[0230] Example 31

[0231] This example provides an α-diimine palladium complex Pd12, R1, R2, R3, R4, R5, and R6 are methyl;

[0232]

[0233] A mixture of a-diimine ligand L1-6 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd12. (0.24 g, 90 % yield).

[0234] Example 32

[0235] This example provides a kind of α-diimine palladium complex Pd13, R1, R2, R3, R4, R5 and R6 are methyl;

[0236]

[0237] A mixture of catalyst Pd12 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and after filtration and drying, a red-brown solid, Pd13, was obtained. (190 mg, 94% yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 32.

[0238] Example 33

[0239] This example provides a kind of α-diimine ligand L1-7, R1 and R4 are hydrogen, R2, R3, R5 and R6 are fluorine;

[0240]

[0241] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,4-difluoroaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5100 g, yield 60%).

[0242] Example 34

[0243] This example provides a kind of α-diimine nickel complex Ni14, R1 and R4 are hydrogen, R2, R3, R5 and R6 are fluorine; X is bromine;

[0244]

[0245] A mixture of α-diimine ligand L1-7 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Ni14. (0.24 g, 90% yield)

[0246] Example 35

[0247] This example provides an α-diimine nickel complex Ni15, R1and R4are hydrogen, R2, R3, R5and R6are fluorine; X is bromine;

[0248]

[0249] A mixture of catalyst Ni14 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, i.e. Ni15. (188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0250] Example 36

[0251] This example provides an α-diimine palladium complex Pd14, R1and R4are hydrogen, R2, R3, R5and R6are fluorine;

[0252]

[0253] A mixture of α-diimine ligand L1-7 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd14. (0.24 g, 90% yield).

[0254] Example 37

[0255] This example provides an α-diimine palladium complex Pd15, R1and R4are hydrogen, R2, R3, R5and R6are fluorine;

[0256]

[0257] A mixture of catalyst Pd 19 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μιηοΐ) was stirred in 10 mL of dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL of hexane, and a red-brown solid, Pd 15, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst with a polymerization degree n of 39.

[0258] Example 38

[0259] This example provides an α-diimine ligand L1-8, R1, R2, R4 and R5 are methyl, R3 and R6 are methoxy;

[0260]

[0261] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,6-dimethyl-4-methoxyaniline (0.6317 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile material was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and oven dried (0.5227 g, 57% yield).

[0262] Example 39

[0263] This example provides an α-diimine nickel complex Ni 16, R1, R2, R4 and R5 are methyl, R3 and R6 are methoxy; X is bromide;

[0264]

[0265] A mixture of α-diimine ligand L1-8 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL of dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid. (0.24 g, 90% yield).

[0266] Example 40

[0267] This example provides an α-diimine nickel complex Ni 17, R1, R2, R4 and R5 are methyl, R3 and R6 are methoxy; X is bromide;

[0268]

[0269] A mixture of catalyst Ni17(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e. Ni17, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 8.

[0270] Example 41

[0271] This example provides an α-diimine palladium complex Pd16, R1, R2, R4 and R5 are methyl, and R3 and R6 are methoxy;

[0272]

[0273] A mixture of α-diimine ligand L1-8(0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25°C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd16. (0.24 g, 90% yield).

[0274] Example 42

[0275] This example provides an α-diimine palladium complex Pd17, R1, R2, R4 and R5 are methyl, and R3 and R6 are methoxy;

[0276]

[0277] A mixture of catalyst Pd16(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e. Pd17, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0278] Example 43

[0279] This example provides an α-diimine ligand L1-9, R1 and R4 are hydrogen, and R2, R3, R5 and R6 are chlorine;

[0280]

[0281] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 2,4-dichloroaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5100 g, 60% yield).

[0282] Example 44

[0283] This example provides an alpha-diimine nickel complex Ni18, R1and R4are hydrogen, R2, R3, R5and R6are chloro; X is bromo;

[0284]

[0285] A mixture of alpha-diimine ligand L1-9 (0.17 g, 0.41 mmol) and (DME)NiBr2(130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni18. (0.24 g, 90% yield)

[0286] Example 45

[0287] This example provides an alpha-diimine nickel complex Ni19, R1and R4are hydrogen, R2, R3, R5and R6are chloro; X is bromo;

[0288]

[0289] A mixture of catalyst Ni18 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, which was Ni19. (188 mg, 94% yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0290] Example 46

[0291] This example provides an alpha-diimine palladium complex Pd18, R1and R4are hydrogen, R2, R3, R5and R6are chloro;

[0292]

[0293] A mixture of a-diimine ligand L1-9 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd18. (0.24 g, 90% yield).

[0294] Example 47

[0295] This example provides a kind of α-diimine palladium complex Pd19, R1 and R4 are hydrogen, R2, R3, R5 and R6 are chlorine;

[0296]

[0297] A mixture of catalyst Pd18 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Pd19, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 39.

[0298] Example 48

[0299] This example provides a kind of α-diimine ligand L1-10, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy;

[0300]

[0301] Norbornene-4,5-dione (0.2853 g, 2.336 mmol) and 4-methoxyaniline (0.6317 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5227 g, yield 57%).

[0302] Example 49

[0303] This example provides a kind of α-diimine nickel complex Ni20, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy; X is bromine;

[0304]

[0305] A mixture of α-diimine ligand L1-10 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid. (0.24 g, 90 % yield).

[0306] Example 50

[0307] This example provides an α-diimine nickel complex Ni21, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy; X is bromide;

[0308]

[0309] A mixture of catalyst Ni20 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Ni21, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 8.

[0310] Example 51

[0311] This example provides an α-diimine palladium complex Pd20, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy;

[0312]

[0313] A mixture of α-diimine ligand L1-10 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd20. (0.24 g, 90 % yield).

[0314] Example 52

[0315] This example provides an α-diimine palladium complex Pd21, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy;

[0316]

[0317] A mixture of catalyst Pd20 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL of dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL of hexane, and a red-brown solid, Pd21, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0318] Example 53

[0319] This example provides an α-diimine ligand L2-1, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen;

[0320]

[0321] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,6-dimethylaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5152 g, yield 58%).

[0322] Example 54

[0323] This example provides an α-diimine nickel complex Ni22, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen; X is bromine;

[0324]

[0325] A mixture of α-diimine ligand L2-1 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL of dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Ni22. (0.24 g, 90 % yield).

[0326] Example 55

[0327] This example provides an α-diimine nickel complex Ni23, R1, R2, R4 and R5 are methyl, R3 and R6 are hydrogen; X is bromine;

[0328]

[0329] A mixture of catalyst Ni22(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e., Ni23, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0330] Example 56

[0331] This example provides an α-diimine palladium complex Pd22, R1, R2, R4 and R5 are methyl, and R3 and R6 are hydrogen;

[0332]

[0333] A mixture of α-diimine ligand L2-1(0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25°C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e., Pd22. (0.24 g, 90% yield).

[0334] Example 57

[0335] This example provides an α-diimine palladium complex Pd23, R1, R2, R4 and R5 are methyl, and R3 and R6 are hydrogen;

[0336]

[0337] A mixture of catalyst Pd22(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e., Pd23, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0338] Example 58

[0339] This example provides an α-diimine ligand L2-2, R1, R2, R4 and R5 are isopropyl, and R3 and R6 are hydrogen;

[0340]

[0341] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,6-diisopropylaniline (0.8283 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.7252 g, 63% yield).

[0342] Example 59

[0343] This example provides an α-diimine nickel complex Ni24, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen; X is bromide;

[0344]

[0345] A mixture of α-diimine ligand L2-2 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni24. (0.24 g, 90 % yield).

[0346] Example 60

[0347] This example provides an α-diimine nickel complex Ni25, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen; X is bromide;

[0348]

[0349] A mixture of catalyst Ni24 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, which was Ni25, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0350] Example 61

[0351] This example provides an α-diimine palladium complex Pd24, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;

[0352]

[0353] A mixture of α-diimine ligand L2-2 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd24. (0.24 g, 90 % yield).

[0354] Example 62

[0355] This example provides an α-diimine palladium complex Pd25, R1, R2, R4 and R5 are isopropyl, R3 and R6 are hydrogen;

[0356]

[0357] A mixture of catalyst Pd24 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Pd25, was obtained after filtration and drying. (190 mg, 94 % yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 32.

[0358] Example 63

[0359] This example provides an α-diimine ligand L2-3, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl;

[0360]

[0361] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,6-dimethyl-4-hydroxy- aniline (0.6317 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.3912 g, yield 41 %).

[0362] Example 64

[0363] This example provides an α-diimine nickel complex Ni26, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl; X is bromine;

[0364]

[0365] A mixture of α-diimine ligand L2-3 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Ni26. (0.24 g, 90 % yield).

[0366] Example 65

[0367] This example provides an α-diimine nickel complex Ni27, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl; X is bromide;

[0368]

[0369] A mixture of catalyst Ni26 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, i.e. Ni27. (188 mg, 94 % yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0370] Example 66

[0371] This example provides an α-diimine palladium complex Pd26, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl;

[0372]

[0373] A mixture of α-diimine ligand L2-3 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd26. (0.24 g, 90 % yield).

[0374] Example 67

[0375] This example provides an α-diimine palladium complex Pd27, R1, R2, R4 and R5 are methyl, R3 and R6 are hydroxyl;

[0376]

[0377] A mixture of catalyst Pd26 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μιηοΐ) was stirred in 10 mL of dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL of hexane, and a red-brown solid, Pd27, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst with a polymerization degree n of 33.

[0378] Example 68

[0379] This example provides an α-diimine nickel complex Ni28, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen; X is bromide;

[0380]

[0381] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,6-diphenylphenylamine (1.1462 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile material was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and oven dried (1.014 g, 69% yield).

[0382] Example 69

[0383] This example provides an α-diimine nickel complex Ni28, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen; X is bromide;

[0384]

[0385] A mixture of α-diimine ligand L2-4 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL of dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Ni28. (0.24 g, 90% yield).

[0386] Example 70

[0387] This example provides an α-diimine nickel complex Ni28, R1, R2, R4 and R5 are phenyl, R3 and R6 are hydrogen; X is bromide;

[0388]

[0389] A mixture of catalyst Ni28(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e. Ni29, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 9.

[0390] Example 71

[0391] This example provides an α-diimine palladium complex Pd28, R1, R2, R4 and R5 are phenyl, and R3 and R6 are hydrogen;

[0392]

[0393] A mixture of α-diimine ligand L2-4(0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25°C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd28. (0.24 g, 90 % yield).

[0394] Example 72

[0395] This example provides an α-diimine palladium complex Pd29, R1, R2, R4 and R5 are phenyl, and R3 and R6 are hydrogen;

[0396]

[0397] A mixture of catalyst Pd28(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e. Pd29, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 29.

[0398] Example 73

[0399] This example provides an α-diimine ligand L2-5, R1, R2, R4 and R5 are benzhydryl, and R3 and R6 are methyl;

[0400]

[0401] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,6-dibenzyl-4-methylaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5152 g, 58% yield).

[0402] Example 74

[0403] This example provides an α-diimine nickel complex Ni30, R1, R2, R4 and R5 are dibenzyl, R3 and R6 are methyl; X is bromide;

[0404]

[0405] A mixture of α-diimine ligand L2-5 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni30. (0.24 g, 90 % yield).

[0406] Example 75

[0407] This example provides an α-diimine nickel complex Ni31, R1, R2, R4 and R5 are dibenzyl, R3 and R6 are methyl; X is bromide;

[0408]

[0409] A mixture of catalyst Ni30 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, which was Ni31, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0410] Example 76

[0411] This example provides an α-diimine palladium complex Pd30, R1, R2, R4 and R5 are dibenzyl, R3 and R6 are methyl;

[0412]

[0413] A mixture of a-diimine ligand L2-5 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd30. (0.24 g, 90 % yield).

[0414] Example 77

[0415] This example provides a kind of α-diimine palladium complex Pd31, R1, R2, R4 and R5 are benzhydryl, R3 and R6 are methyl;

[0416]

[0417] A mixture of catalyst Pd30 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Pd31, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0418] Example 78

[0419] This example provides a kind of α-diimine ligand L2-6, R1, R2, R4 and R5 are methyl, R3 and R6 are methyl;

[0420]

[0421] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,4,6-trimethylaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5152 g, yield 58 %).

[0422] Example 79

[0423] This example provides a kind of α-diimine nickel complex Ni32, R1, R2, R4 and R5 are methyl, R3 and R6 are methyl; X is bromine;

[0424]

[0425] A mixture of α-diimine ligand L2-6 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Ni32. (0.24 g, 90 % yield).

[0426] Example 80

[0427] This example provides an α-diimine nickel complex Ni33, R1, R2, R4 and R5 are methyl, R3 and R6 are methyl; X is bromide;

[0428]

[0429] A mixture of catalyst Ni32 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, i.e. Ni33. (188 mg, 94 % yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0430] Example 81

[0431] This example provides an α-diimine palladium complex Pd32, R1, R2, R4 and R5 are methyl, R3 and R6 are methyl;

[0432]

[0433] A mixture of α-diimine ligand L2-6 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd32. (0.24 g, 90 % yield).

[0434] Example 82

[0435] This example provides an α-diimine palladium complex Pd33, R1, R2, R4 and R5 are methyl, R3 and R6 are methyl;

[0436]

[0437] A mixture of catalyst Pd32(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL of dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL of hexane, and a red-brown solid, Pd33, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0438] Example 83

[0439] This example provides an α-diimine nickel complex Ni34, R1and R4are hydrogen, R2, R3, R5and R6are fluorine; X is bromine;

[0440]

[0441] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,4-difluoroaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile material was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and oven dried (0.5152 g, 58% yield).

[0442] Example 84

[0443] This example provides an α-diimine nickel complex Ni34, R1and R4are hydrogen, R2, R3, R5and R6are fluorine; X is bromine;

[0444]

[0445] A mixture of α-diimine ligand L2-7(0.17 g, 0.41 mmol) and (DME)NiBr2(130 mg, 0.42 mmol) was stirred in 20 mL of dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered, and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Ni34. (0.24 g, 90% yield).

[0446] Example 85

[0447] This example provides an α-diimine nickel complex Ni34, R1and R4are hydrogen, R2, R3, R5and R6are fluorine; X is bromine;

[0448]

[0449] A mixture of catalyst Ni34(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e. Ni35, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0450] Example 86

[0451] This example provides an α-diimine palladium complex Pd34, R1and R4are hydrogen, and R2, R3, R5and R6are fluorine;

[0452]

[0453] A mixture of α-diimine ligand L2-7(0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25°C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd34. (0.24 g, 90 % yield).

[0454] Example 87

[0455] This example provides an α-diimine palladium complex Pd35, R1and R4are hydrogen, and R2, R3, R5and R6are fluorine;

[0456]

[0457] A mixture of catalyst Pd34(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, i.e. Pd35, was obtained after filtration and drying. (188 mg, 94% yield). The catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0458] Example 88

[0459] This example provides an α-diimine ligand L2-8, R1, R2, R4and R5are methyl, and R3and R6are methoxy;

[0460]

[0461] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 4-methoxy-2,6-dimethylaniline (0.8283 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and dried (0.7252 g, 63% yield).

[0462] Example 89

[0463] This example provides an alpha-diimine nickel complex Ni36, R1, R2, R4 and R5 are methyl, R3 and R6 are methoxy; X is bromide;

[0464]

[0465] A mixture of alpha-diimine ligand L2-8 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, which was Ni36. (0.24 g, 90 % yield).

[0466] Example 90

[0467] This example provides an alpha-diimine nickel complex Ni37, R1, R2, R4 and R5 are methyl, R3 and R6 are methyl; X is bromide;

[0468]

[0469] A mixture of catalyst Ni36 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, which was Ni37. (188 mg, 94 % yield). This catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0470] Example 91

[0471] This example provides an alpha-diimine palladium complex Pd36, R1, R2, R4 and R5 are methyl, R3 and R6 are methoxy;

[0472]

[0473] A mixture of a-diimine ligand L2-8 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Pd36. (0.24 g, 90 % yield).

[0474] Example 92

[0475] This example provides a kind of α-diimine palladium complex Pd37, R1, R2, R4 and R5 are methyl, R3 and R6 are methoxy group;

[0476]

[0477] A mixture of catalyst Pd36 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid, Pd37, was obtained after filtration and drying. (188 mg, 94 % yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0478] Example 93

[0479] This example provides a kind of α-diimine ligand L2-9, R1 and R4 are hydrogen, R2, R3, R5 and R6 are chlorine;

[0480]

[0481] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 2,4-dichloroaniline (0.5662 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile substances were removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The formed solid was filtered and dried (0.5152 g, yield 58 %).

[0482] Example 94

[0483] This example provides a kind of α-diimine nickel complex Ni38, R1 and R4 are hydrogen, R2, R3, R5 and R6 are chlorine; X is bromine;

[0484]

[0485] A mixture of α-diimine ligand L2-9 (0.17 g, 0.41 mmol) and (DME)NiBr2 (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Ni38. (0.24 g, 90 % yield).

[0486] Example 95

[0487] This example provides an α-diimine nickel complex Ni39, R1and R4are hydrogen, R2, R3, R5and R6are chlorine; X is bromide;

[0488]

[0489] A mixture of catalyst Ni38 (0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, i.e. Ni39. (188 mg, 94 % yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0490] Example 96

[0491] This example provides an α-diimine palladium complex Pd38, R1and R4are hydrogen, R2, R3, R5and R6are chlorine;

[0492]

[0493] A mixture of α-diimine ligand L2-9 (0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25 °C for 72 h. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, i.e. Pd38. (0.24 g, 90 % yield).

[0494] Example 97

[0495] This example provides an α-diimine palladium complex Pd39, R1and R4are hydrogen, R2, R3, R5and R6are chlorine;

[0496]

[0497] A mixture of catalyst Pd38(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μιηοΐ) was stirred in 10 mL of dichloromethane at room temperature for 12 h. After the reaction was completed, the solution was poured into 40 mL of hexane, and a red-brown solid, Pd39, was obtained after filtration and drying. (188 mg, 94% yield). This catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0498] Example 98

[0499] This example provides an α-diimine ligand L2-10, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy;

[0500]

[0501] Cyclooctene-5,6-dione (0.3228 g, 2.336 mmol) and 4-methoxy-2,6-dimethylaniline (0.8283 g, 4.672 mmol) were dissolved in a mixture of methanol (2.5 mL) and formic acid (0.25 mL). The mixture was stirred at room temperature for 24 h. The volatile material was removed, methanol (1.0 mL) was added, and the mixture was cooled to -78 °C. The solid formed was filtered and oven dried (0.7252 g, 63% yield).

[0502] Example 99

[0503] This example provides an α-diimine nickel complex Ni40, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy; X is bromide;

[0504]

[0505] A mixture of α-diimine ligand L2-10 (0.17 g, 0.41 mmol) and (DME)NiBr2(130 mg, 0.42 mmol) was stirred in 20 mL of dichloromethane at 25 °C for 72 h. After the reaction was completed, the mixture was filtered, and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, Ni40. (0.24 g, 90% yield).

[0506] Example 100

[0507] This example provides an α-diimine nickel complex Ni41, R1, R2, R4 and R5 are hydrogen, R3 and R6 are methoxy; X is bromide;

[0508]

[0509] A mixture of catalyst Ni40(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, namely Ni41.(188 mg, 94% yield). The catalyst is a macromolecular nickel catalyst, and the polymerization degree n is 13.

[0510] Example 101

[0511] This example provides an α-diimine palladium complex Pd40, R1, R2, R4 and R5 are hydrogen, and R3 and R6 are methoxy groups.

[0512]

[0513] A mixture of α-diimine ligand L2-10(0.17 g, 0.41 mmol) and (COD)PdMeCl (130 mg, 0.42 mmol) was stirred in 20 mL dichloromethane at 25°C for 72 hours. After the reaction was completed, the solution was filtered and the solvent was evaporated under reduced pressure to obtain a yellow-green solid, namely Pd25.(0.24 g, 90 % yield).

[0514] Example 102

[0515] This example provides an α-diimine palladium complex Pd41, R1, R2, R4 and R5 are hydrogen, and R3 and R6 are methoxy groups.

[0516]

[0517] A mixture of catalyst Pd40(0.5 g, 0.76 mmol) and Grubbs II catalyst (6.4 mg, 7.5 μmol) was stirred in 10 mL dichloromethane at room temperature for 12 hours. After the reaction was completed, the solution was poured into 40 mL hexane, and a red-brown solid was obtained after filtration and drying, namely Pd41.(188 mg, 94% yield). The catalyst is a macromolecular palladium catalyst, and the polymerization degree n is 28.

[0518] Application Example 1 - Nickel catalyst catalyzing ethylene homopolymerization

[0519] A 350 mL glass pressure reactor connected to a high pressure gas line was first dried under vacuum at 90 °C for at least 1 hour. The reactor was then adjusted to 30 °C, 50 °C, 70 °C and 90 °C, 98 mL of toluene and 500 equivalents of co-catalyst (MAO) were added to the reactor under inert atmosphere, then the nickel catalyst (1 μmol) dissolved in 2 mL of dichloromethane or chloroform was injected into the polymerization system by syringe. With rapid stirring (450 rpm or more), ethylene was introduced and maintained at 8 atm. After 30 minutes, the pressure reactor was evacuated, the polymerization reaction was quenched by adding a large amount of acidic methanol (or ethanol) (5% or more of hydrochloric acid in alcohol solution), the polymer was filtered, and dried to constant weight in a vacuum oven.

[0520] The data of the effect of different temperatures during MAO activation and the polymerization degree of macromolecular nickel catalyst I on ethylene polymerization are shown in Table 1 below (all data are based on at least two parallel experiments (unless otherwise specified). Activity: in 10 6 gmol -1 h -1 M n Mn is the number average molecular weight, the polymer molecular weight and molecular weight distribution are determined by GPC at 150 °C in 1,2,4-trichlorobenzene, relative to polystyrene standards. Branching degree = the number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectrum).

[0521] Table 1

[0522] No. Catalyst Temperature (°C) Yield (g) Activity M n (kg / mol)]]> Molecular weight distribution Degree of branching 1 Ni3 30 2.2 4.4 53.0 2.65 104 2 Ni3 50 1.4 2.8 39.2 2.57 110 3 Ni3 70 1.3 2.7 26.5 2.92 111 4 Ni3 90 trace - - - - 5 Ni4 30 5.5 11.0 83.8 2.67 67 6 Ni4 50 4.9 9.8 72.0 2.86 89 7 Ni4 70 3.8 7.6 53.0 2.10 90 8 Ni4 90 1.6 3.2 23.5 1.94 83 9 Ni5 30 10.1 20.2 201.0 2.43 48 10 Ni5 50 5.7 11.4 77.4 2.56 93 11 Ni5 70 4.9 9.7 69.3 2.67 99 12 Ni5 90 2.2 4.5 30.2 1.95 96

[0523] From the data in Table 1, under the same conditions, with the increase of the polymerization degree of Ni3~Ni5 catalyst, the activity of catalyzing ethylene homopolymerization increases significantly, and the molecular weight increases significantly; and for the same catalyst, with the increase of temperature, the activity decreases, the molecular weight decreases, and the branching degree increases. The monomolecular catalyst Ni3 loses activity at 90 °C, but the macromolecular nickel catalyst Ni4 and Ni5 still have high activity at 90 °C.

[0524] The data of the effect of different temperatures during MAO activation and the axial steric hindrance of macromolecular nickel catalyst I on ethylene polymerization are shown in Table 2 below (all data are based on at least two parallel experiments (unless otherwise specified). Activity: in 10 6 gmol -1 h -1 M n Mn is the number average molecular weight, the polymer molecular weight and molecular weight distribution are determined by GPC at 150 °C in 1,2,4-trichlorobenzene, relative to polystyrene standards. Branching degree = the number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectrum).

[0525] Table 2

[0526] No. Catalyst Temperature (°C) Yield (g) Activity M n (kg / mol)]]> Molecular weight distribution Degree of branching 1 Ni2 30 2.3 4.6 4.5 2.96 81 2 Ni2 50 1.8 3.6 4.3 3.08 85 3 Ni2 70 1.6 3.2 4.1 3.09 88 4 Ni2 90 0.6 1.2 3.4 3.50 89 5 Ni9 30 4.5 9.0 115.0 2.19 59 6 Ni9 50 3.6 7.2 96.4 2.29 64 7 Ni9 70 2.8 5.6 87.4 2.35 73 8 Ni9 90 1.0 2.0 65.3 2.52 83 9 Ni5 30 13.6 27.2 380.4 2.07 50 10 Ni5 50 10.8 21.6 252.2 2.18 60 11 Ni5 70 7.5 15.0 124.0 2.18 72 12 Ni5 90 3.1 6.2 91.6 2.29 79

[0527] From the data in Table 2, under the same conditions, as the axial steric hindrance of Ni2, Ni9, Ni5 catalysts increases, the activity of catalyzing ethylene homopolymerization increases significantly, and the molecular weight increases significantly; and for the same catalyst, as the temperature increases, the activity decreases, the molecular weight decreases, and the branching degree increases. Application Example 2 - Nickel catalyst catalyzing ethylene homopolymerization

[0528] First, a 350 mL glass pressure reactor connected to a high-pressure gas pipeline was vacuum dried at 90°C for at least 1 hour. Then the reactor was adjusted to 30°C, 50°C, 70°C and 90°C, 98 mL of toluene and 500 equivalents of cocatalyst (Et2AlCl) were added to the reactor under an inert atmosphere, and then the nickel catalyst (1 μmol) was dissolved in 2 mL of dichloromethane or chloroform and injected into the polymerization system by a syringe. Under rapid stirring (more than 450 rpm), ethylene was introduced and maintained at 8 atm. After 30 minutes, the pressure reactor was evacuated, a large amount of acidic methanol (or ethanol) (5% hydrochloric acid alcohol solution) solution was added to quench the polymerization reaction, the polymer was filtered, and dried to constant weight in a vacuum oven.

[0529] The data of the effect of different temperatures during Et2AlCl activation and the polymerization degree of macromolecular nickel catalyst I on ethylene polymerization are shown in Table 3 below (all data are based on at least two parallel experiments (unless otherwise specified). Activity: in 10 6 g mol -1 h -1 M n is the number average molecular weight, the molecular weight and molecular weight distribution of the polymer are determined by GPC at 150°C in 1,2,4-trichlorobenzene, relative to polystyrene standards. Branching degree = number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectrum).

[0530] Table 3

[0531] No. Catalyst Temperature (°C) Yield (g) Activity M n (kg / mol)]]> Molecular weight distribution Degree of branching 1 Ni3 30 2.61 5.22 41.1 1.78 102 2 Ni3 50 1.29 2.58 33.8 2.00 104 3 Ni3 70 0.16 0.32 31.7 1.78 108 4 Ni3 90 trace - - - - 5 Ni4 30 7.75 15.5 56.4 2.04 81 6 Ni4 50 6.12 12.2 48.0 2.11 94 7 Ni4 70 4.53 9.06 42.5 2.02 96 8 Ni4 90 1.04 2.08 23.5 1.94 103 9 Ni5 30 12.5 25.1 63.2 1.78 72 10 Ni5 50 11.4 22.8 49.9 1.88 79 11 Ni5 70 6.45 12.9 48.4 1.99 87 12 Ni5 90 2.87 5.74 27.5 1.88 102

[0532] From the data in Table 3, under the same conditions, as the polymerization degree of Ni3~Ni5 catalysts increases, the activity of catalyzing ethylene homopolymerization increases significantly, and the molecular weight increases significantly; and for the same catalyst, as the temperature increases, the activity decreases, the molecular weight decreases, and the branching degree increases. Monomolecular catalyst Ni3 loses activity at 90°C, but macromolecular nickel catalysts Ni4 and Ni5 still have high activity at 90°C.

[0533] The hydrogen spectrum of the polymer prepared in Table 3 No. 11 is as followsFigure 2 As shown, the obtained polymer has a large number of branches, which may indicate that it is an elastomer with good performance.

[0534] Stress-strain tests were performed on the polymers prepared according to numbers 5, 9, and 10 in Table 3. The test methods are as follows:

[0535] Polymer strips with a length of 15 mm, a width of 2 mm, and a thickness of 1 mm were prepared and cut out, and subjected to the tensile test of 100 N according to GB-T 1040.3 2006.

[0536] Test results are as follows Figure 3 As shown, it can be seen that Ni5 can produce polyethylene elastomers with higher elongation at break than Ni4, and the degree of branching of the elastomer can be adjusted by temperature, with higher temperature resulting in higher branching.

[0537] Elastic recovery tests were performed on the polymers prepared corresponding to item 5 in Table 3. The test methods are as follows:

[0538] Polymer strips with a length of 15 mm, a width of 2 mm, and a thickness of 1 mm were prepared and cut, and subjected to a fixed cycle of 100 N according to GB-T 1040.3 2006.

[0539] Test results are as follows Figure 4 As shown in the table, sample number 5 in Table 3 has good elastic recovery performance, with an elastic recovery rate of 63%.

[0540] The effects of different temperatures and axial steric hindrance of macromolecular nickel catalyst I on ethylene polymerization during Et2AlCl activation are shown in Table 4 below (all data are based on at least two parallel experiments (unless otherwise stated). Activity: at 10 6 g mol -1 h -1 Unit: M n Number average molecular weight, polymer molecular weight and molecular weight distribution were determined by GPC in 1,2,4-trichlorobenzene at 150°C, relative to polystyrene standards. Branching degree = number of branches per 1000 carbon atoms, determined by 1H NMR spectroscopy.

[0541] Table 4

[0542] No. Catalyst Temperature (°C) Yield (g) Activity M n (kg / mol)]]> Molecular weight distribution Degree of branching 1 Ni2 30 2.1 4.2 6.3 2.86 82 2 Ni2 50 1.5 3.0 6.0 3.20 84 3 Ni2 70 1.2 2.4 5.8 3.52 86 4 Ni2 90 0.3 0.6 3.7 3.56 87 5 Ni9 30 4.8 9.6 108.3 2.03 66 6 Ni9 50 3.5 7.0 76.2 2.08 73 7 Ni9 70 2.7 5.4 55.6 2.00 77 8 Ni9 90 1.2 2.4 45.0 2.32 88 9 Ni5 30 15.8 31.6 320.7 1.99 46 10 Ni5 50 12.4 24.8 222.8 2.20 55 11 Ni5 70 8.7 17.4 130.5 2.28 62 12 Ni5 90 4.4 8.8 81.0 2.33 71

[0543] As shown in Table 4, under the same conditions, the activity of Ni2, Ni9, and Ni5 catalysts in homopolymerization of ethylene increases significantly and the molecular weight increases significantly as the axial steric hindrance increases. Moreover, for the same catalyst, the activity and molecular weight decrease and the degree of branching increases with increasing temperature in the polymerization reaction.

[0544] Example 3 - Ethylene homopolymerization catalyzed by palladium catalysts

[0545] A 350 mL glass pressure reactor connected to a high pressure gas line was first dried under vacuum at 90°C for at least 1 hour. The reactor was then adjusted to 30°C, 50°C, 70°C and 90°C, 98 mL of toluene and 1.2 μmol of NaBArF were added to the reactor under inert atmosphere, and the palladium catalyst (1 μmol) was then dissolved in 2 mL of dichloromethane or chloroform and injected into the polymerization system via a syringe. Ethylene was introduced and maintained at 8 atm under rapid stirring (750 rpm and above). After 30 minutes, the pressure reactor was evacuated, the polymerization was quenched by the addition of a large excess of acidic methanol (or ethanol) (5% HCl in alcohol), the polymer was filtered and dried to constant weight in a vacuum oven.

[0546] The effect of temperature on the polymerization of ethylene with the macromolecular palladium catalyst of structure I I is shown in Table 5 (all data are based on at least two parallel runs (unless otherwise indicated). Activity: in 10 6 gmol -1 h -1 M n Mn is the number average molecular weight, the polymer molecular weight and molecular weight distribution were determined by GPC in 1,2,4-trichlorobenzene at 150°C relative to polystyrene standards. Branching = number of branches per 1000 carbons, determined by proton NMR).

[0547] Table 5

[0548] No. Catalyst Temperature (°C) Yield (g) Activity M n (kg / mol)]]> Molecular weight distribution Degree of branching 1 Pd22 30 2.0 4.0 43.2 1.83 87 2 Pd22 50 1.4 2.8 32.0 2.07 96 3 Pd22 70 1.3 2.7 19.8 2.26 99 4 Pd22 90 0.9 1.8 14.3 2.33 101 5 Pd23 30 3.2 6.4 48.8 1.83 86 6 Pd23 50 1.7 3.4 36.2 1.88 92 7 Pd23 70 1.4 2.8 23.5 2.03 95 8 Pd23 90 1.1 2.2 18.8 2.29 97 9 Pd24 30 2.2 4.4 46.7 1.90 83 10 Pd24 50 1.7 3.4 36.8 1.98 92 11 Pd24 70 0.5 1.0 22.4 1.96 94 12 Pd24 90 0.3 0.6 18.8 1.98 99 13 Pd25 30 3.5 7.1 76.1 1.60 83 14 Pd25 50 2.9 5.7 56.8 1.65 83 15 Pd25 70 1.4 2.8 33.0 1.59 90 16 Pd25 90 0.7 1.5 26.5 1.70 91

[0549] As can be seen from the data in Table 5, under the same conditions, the macromolecular palladium catalysts have higher polymerization activity than the monomeric palladium catalysts, the polymers prepared have higher molecular weight, lower branching and narrower molecular weight distribution.

[0550] Example 4 - Ethylene polymerization scale-up experiments with methylaluminoxane (MAO) activated macromolecular nickel catalysts of structure I

[0551] A 20 L industrial polymerization reactor connected to a high-pressure gas line was first dried under vacuum at 90 °C for at least 1 hour. Then the reactor temperature was adjusted to 65 °C, 13 L of n-hexane and 500 eq of MAO were added to the reactor under inert atmosphere, then the specified amount of nickel catalyst was dissolved in a specific amount of dichloromethane (1 mL of dichloromethane was used for dissolving 1 mol of catalyst) and injected into the polymerization system by a syringe, under rapid stirring, the pressure was quickly raised to 20 bar by the introduction of ethylene. After 1 hour, the pressure in the reactor was evacuated, and the reaction liquid was placed in a stainless steel barrel, then 13 L of acidic ethanol (an ethanol solution containing 5% by mass of hydrochloric acid) was added to quench the polymerization reaction, the polymer was separated, and dried to constant weight in a vacuum oven. The test results are shown in Table 6 below (all data are based on at least two parallel tests (unless otherwise specified). Activity: in 10 6 g mol -1 h -1 M n is the number average molecular weight, the molecular weight and molecular weight distribution of the polymer were determined by GPC at 150 °C in 1,2,4-trichlorobenzene, relative to polystyrene standards. Branching degree = number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectrum).

[0552] Table 6

[0553] No. Catalyst Catalyst amount (pmol) Yield (g) Activity M n (kg / mol)]]> Molecular weight distribution Degree of branching 1 Ni3 100 280 2.8 5.3 2.78 78 2 Ni5 20 240 12.0 - - - 3 Ni5 50 600 12.0 49.5 1.84 87 4 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni5 Ni 100 1000 10.0 49.0 1.86 89

[0554] From the data in Table 6, it can be seen that under scale-up conditions, the macromolecular Ni5 catalyst can produce high-branched polyethylene elastomer with high activity, with the highest activity reaching 12 × 10 6 g mol -1 h -1 , i.e. 18 kg PE / g Cat . In contrast, the monomolecular catalyst Ni3 has lower activity and molecular weight.

[0555] It should be noted that the above acidic ethanol can also be replaced by acidic methanol (a methanol solution containing 5% by mass of hydrochloric acid).

[0556] In summary, the present application has the following advantages:

[0557] (1) Catalyst structure innovation: a class of α-diimine ligands and nickel, palladium catalysts are synthesized, which contain double bonds in the skeleton, and the structure is special;

[0558] (2) Innovation of synthesis route: the intramolecular double bond existing in the ligand skeleton of the macromolecular catalyst can form a macromolecular ligand or catalyst through ring-opening metathesis polymerization, which is highly innovative;

[0559] (3) excellent catalyst performance: a class of macromolecular α-diimine nickel and palladium catalysts were synthesized by ring-opening metathesis polymerization, which significantly improved the polymerization activity and polymer molecular weight. The highest activity was improved by 7.5 times (Table 4, No. 9 vs. No. 1), and the molecular weight was improved by 85 times (Table 3, No. 9 vs. No. 1);

[0560] (4) excellent performance of the prepared polymers: high molecular weight polyethylene elastomers (3.8 million) with certain branching degree (48-111 / 1000C) were prepared, which were prepared with ethylene as a single raw material, and had low cost and excellent tensile and recovery performance, and had very good application prospect.

[0561] The above description of the disclosed embodiments enables those skilled in the art to carry out or use the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A macromolecular α-diimine nickel-palladium catalyst, characterized in that, It has the structure shown in Formula I or II: Formula I; Formula II; Among them, R 1 R 2 R 4 and R 5 Each is independently selected from substituted or unsubstituted C1-C6 alkyl groups and substituted or unsubstituted C6-C30 aryl groups; R 3 and R 6 Each is independently selected from hydrogen, hydroxyl, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy; M is either nickel or palladium; X is a halogen, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C6-C30 aryl group; The value of n ranges from 2 to 1000; In the above-mentioned substituted or unsubstituted form, the substituted group is selected from C1-C3 alkyl groups or C6-C18 aryl groups.

2. The macromolecular α-diimine nickel / palladium catalyst according to claim 1, characterized in that, The R 1 R 2 R 4 and R 5 Each is independently selected from substituted or unsubstituted C1-C4 alkyl groups and substituted or unsubstituted C6-C20 aryl groups; R 3 and R 6 Each is independently selected from hydrogen, hydroxyl, halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkoxy; X is a halogen, a substituted or unsubstituted C1-C4 alkyl group, or a substituted or unsubstituted C6-C20 aryl group.

3. The macromolecular α-diimine nickel / palladium catalyst according to claim 1 or 2, characterized in that, The R 1 R 2 R 4 and R 5 Each is independently selected from methyl, phenyl, isopropyl, or diphenylmethyl; R 3 and R 6 Each is independently selected from hydrogen, methyl, hydroxyl, halogen, or methoxy; X is a halogen, a substituted or unsubstituted C1-C3 alkyl group, or a substituted or unsubstituted C6-C18 aryl group.

4. The macromolecular α-diimine nickel / palladium catalyst according to claim 1, characterized in that, The macromolecular α-diimine nickel and palladium catalysts are selected from any one of the following formulas: 。 5. A method for preparing a macromolecular α-diimine nickel / palladium catalyst as described in any one of claims 1 to 4, characterized in that, Methods for preparing macromolecular α-diimine nickel and palladium catalysts having the structure shown in Formula I or Formula ⅠⅠ include: S1-1: Mix and react norbornene or cyclooctenene with the substituted aromatic amine shown in formula A to obtain the compound shown in formula L1 or formula L2. S2-1: Mix the compound shown in formula L1 or L2 with a nickel source or a palladium source and react them to obtain the compound shown in formula C1 or C2; S3-1: The compounds shown in formula C1 or formula C2 are polymerized in the presence of a catalyst to obtain macromolecular α-diimine nickel and palladium catalysts with the structures shown in formula I or formula ⅠⅠ. Formula A; Formula L1; Formula C1; Formula L2; Formula C2; or S1-2: Following the method in S1-1, the compound shown in formula L1 or formula L2 is obtained; S2-2: The compounds represented by formula L1 or L2 are polymerized in the presence of a catalyst to obtain the compounds represented by formula L1-P or L2-P. S3-2: Mix the compound represented by formula L1-P or L2-P with a nickel source or a palladium source and react them to obtain the macromolecular α-diimine nickel or palladium catalyst represented by formula I or formula ⅠⅠ; Formula L1-P; Formula L2-P.

6. The preparation method according to claim 5, characterized in that, The molar ratio of norbornene or cyclooctenedone to the substituted aromatic amine shown in Formula A is 1:1 to 1:

20. The molar ratio of the compound represented by formula L1 or L2 to the nickel source or palladium source is 1:1 to 1:10; The molar ratio of the compound represented by formula C1 or C2 to the catalyst is 10:1 to 1000:1; The molar ratio of the compound represented by formula L1 or L2 to the catalyst is 10:1 to 1000:1; The molar ratio of the compound represented by formula L1-P or formula L2-P to the nickel source or palladium source is 1:n.

7. The preparation method according to claim 5 or 6, characterized in that, The reaction temperature in step S1-1 is 20~80℃, and the reaction time is 2~10 h; The temperature of the reaction in step S2-1 or step S3-2 is independently 15~30℃, and the reaction time is independently 40~90 h; The polymerization temperature in step S2-2 or step S3-1 is independently 15~30℃, and the polymerization time is independently 5~20 h.

8. The preparation method according to claim 5, characterized in that, The nickel source is selected from nickel bromide in ethylene glycol dimethyl ether and / or nickel chloride in ethylene glycol dimethyl ether. The palladium source is selected from chloro(1,5-cyclooctadiene)methylpalladium(II); The catalyst is selected from any one or more of Grubbs I catalyst, Grubbs II catalyst, Grubbs III catalyst, Hoveyda-Grubbs I catalyst, or Hoveyda-Grubbs II catalyst.

9. The application of the macromolecular α-diimine nickel or palladium catalyst according to any one of claims 1 to 4, or the macromolecular α-diimine nickel or palladium catalyst prepared by the preparation method according to any one of claims 5 to 8, in ethylene polymerization.

10. The application according to claim 9, characterized in that, The application temperature of the macromolecular α-diimine nickel and palladium catalyst is ≥0℃.

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