α-Diimine ligand compounds, their metal complexes, α-diimine metal-supported catalysts and their applications

Abstract

The present disclosure relates to an α-diimine ligand compound, its metal complex, an α-diimine metal-supported catalyst and its application, belonging to the fields of catalytic olefin polymerization and synthesis of high molecular polyolefin materials. The ligand compound has the structural formula shown in formula (I), wherein R1, R2, R3, and R4 are each independently selected from any one of C1-C 11 alkyl, substituted or unsubstituted diphenylmethyl, and hydrogen; R5 is selected from any one of methoxy, hydroxy, and sodium oxy substituents. When there is a substituent on the diphenylmethyl, the substituent is selected from C1-C 11 alkyl, C1-C 11 alkoxy, and C2-C 11 alkenyl. The ligand compound of the present disclosure regulates the steric hindrance by the selection of the backbone of the diimine and the R5 group, and inhibits the chain walking of the subsequently formed metal complex.

Description

Technical Field

[0001] The present disclosure relates to the fields of catalytic olefin polymerization and synthetic high molecular polyolefin materials, and specifically relates to an α-diimine ligand compound, its metal complex, an α-diimine metal-supported catalyst, and their applications. Background Art

[0002] Polyethylene is one of the polymers with relatively large annual output and practicality. Ethylene, which is relatively inexpensive and easy to prepare, can be converted into various materials, such as plastics, fibers, and elastomers, through a relatively simple insertion method. Currently, by introducing some polar groups into the main chain of polyolefins, this material becomes more suitable for different fields of daily life, such as drug delivery, nanoelectronics, coatings, adhesives, and primers. It is still necessary to explore the development of a new structure and the introduction of some adjustable polar monomers.

[0003] In the related art, in this process of structural modification evolution, the ligand steric factor plays a relatively crucial role in different types of late transition metal catalysts, such as salicylaldimine, phosphonate, pyridineoximeimine, imine / phosphine oxide, and iminopyridyl. However, the above-mentioned imine catalysts still have low thermal stability and are relatively prone to produce highly branched oily and low molecular weight polymers.

[0004] In summary, the imine-based metal catalysts in the related art have low thermal stability. During the catalytic polymerization reaction, it is relatively difficult to control the molecular weight and structure of the prepared polymer, and it is difficult to promote production. Summary of the Invention

[0005] In view of this, the present disclosure proposes to construct an α-diimine ligand compound containing a methoxy, hydroxyl, or sodium oxy substituent, which can increase the steric hindrance of the ligand in the metal, not only inhibiting chain transfer but also restricting the rotation of the N-aryl moiety at higher temperatures, thereby facilitating the preparation of polymers with low branching degrees and higher molecular weights.

[0006] One object of the present disclosure is to provide an α-diimine ligand compound.

[0007] Another object of the present disclosure is to provide an α-diimine metal complex.

[0008] Another object of the present disclosure is to provide an α-diimine metal-supported catalyst prepared using the above metal complex.

[0009] Another object of the present disclosure is to provide an application of the above α-diimine metal-supported catalyst.

[0010] The above objects of the present disclosure are achieved through the following technical solutions.

[0011] According to an embodiment of one aspect of the present disclosure, there is provided an α-diimine ligand compound of formula I, wherein R1, R2, R3, and R4 are each independently selected from any one of C1-C 11 alkyl, substituted or unsubstituted benzhydryl, and hydrogen; R5 is selected from any one of methoxy, hydroxy, and sodium oxygen substituents. When there are substituents on the benzhydryl, the substituents are selected from C1-C 11 alkyl, C1-C 11 alkoxy, and C2-C 11 alkenyl.

[0012]

[0013] In some embodiments, R1, R2, R3, and R4 are each independently selected from one of the following structures:

[0014]

[0015] In some embodiments, the above ligand compound includes compounds having the structures shown in formulae I1 to I 12 as follows:

[0016]

[0017] According to an embodiment of another aspect of the present disclosure, there is provided an α-diimine metal complex of formula II, wherein M includes any one of nickel and palladium; X includes at least one of methyl, chlorine, and bromine; R1, R2, R3, and R4 are each independently selected from any one of C1-C 11 alkyl, substituted or unsubstituted benzhydryl, and hydrogen; R5 is selected from any one of methoxy, hydroxy, and sodium oxygen substituents. When there are substituents on the benzhydryl, the substituents are selected from C1-C 11 alkyl, C1-C 11 alkoxy, and C2-C 11 alkenyl.

[0018]

[0019] In some embodiments, the definitions of R1, R2, R3, and R4 are as described above and will not be elaborated herein.

[0020] In some embodiments, the above α-diimine metal complex includes compounds having the structures shown in formulae II1 to II 10 as follows:

[0021]

[0022]

[0023] According to an embodiment of another aspect of the present disclosure, an α-diimine metal-supported catalyst is provided, which is prepared by using the above metal complex and a carrier, wherein the metal complex is supported on the carrier.

[0024] In some embodiments, the carrier includes at least one of silica, magnesium chloride, or aluminum oxide.

[0025] According to an embodiment of yet another aspect of the present disclosure, an application of the above-supported catalyst in the polymerization reaction of C2-C 11 olefin monomers is provided.

[0026] In some embodiments, the polymerization reaction of C2-C 11 olefin monomers includes: adding a cocatalyst and C2-C 11 olefin monomers to an organic solvent, and then injecting the supported catalyst, so that the C2-C 11 olefin monomers undergo a coordination polymerization reaction.

[0027] In some embodiments, the organic solvent includes at least one of toluene, benzene, or n-heptane; the cocatalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum, an alkali metal, or an alkali metal salt; the C2-C 11 olefin monomers include at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene, or 1-octene.

[0028] In some embodiments, the coordination polymerization reaction includes homopolymerization and / or copolymerization of C2-C 11 olefin monomers.

[0029] Based on the above technical solutions, the α-diimine ligand compound, its metal complex, the α-diimine metal-supported catalyst, and their applications provided by the present disclosure have one or some of the following beneficial effects:

[0030] The present disclosure utilizes the synergistic effect of the α-diamine backbone and the methoxy, hydroxyl, or sodium oxy substituents of the R5 group to jointly construct a large steric hindrance, which can assist in controlling the subsequent metal-nitrogen coordination within a very small space range, thereby reducing the uncontrolled chain walking reaction of the metal group and improving the selectivity and yield during metal coordination. Moreover, it can restrict the rotation of the N-aryl moiety at high temperatures, prevent the occurrence of unnecessary side reactions, and reduce the degree of branching of the subsequently prepared polymer. Additionally, it is beneficial to achieve the regulation of the same interaction between the ligand compound and its metal ligand in the subsequent catalytic reaction, thereby improving the efficiency and controllability of the catalytic polymerization reaction, and facilitating the preparation of olefin polymers with a lower degree of branching and a higher molecular weight. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The following further describes the present disclosure in detail with reference to the accompanying drawings.

[0032] Figure 1 Shows the 1H NMR spectrum of 2,4-dibenzoyl-6-methoxyaniline in Example 1 of the present disclosure;

[0033] Figure 2 Shows the 13C NMR spectrum of 2,4-dibenzoyl-6-methoxyaniline in Example 1 of the present disclosure;

[0034] Figure 3 Shows the mass spectrum of 2,4-dibenzoyl-6-methoxyaniline in Example 1 of the present disclosure;

[0035] Figure 4 Shows the 1H NMR spectrum of Complex 1 in Example 1 of the present disclosure;

[0036] Figure 5 Shows the 13C NMR spectrum of Complex 1 in Example 1 of the present disclosure;

[0037] Figure 6 Shows the 1H NMR spectrum of Complex 2 in Example 2 of the present disclosure;

[0038] Figure 7 Shows the 13C NMR spectrum of Complex 2 in Example 2 of the present disclosure;

[0039] Figure 8 Shows the mass spectrum of the nickel complex Ni1 in Example 1 of the present disclosure;

[0040] Figure 9 Shows the mass spectrum of the nickel complex Ni3 in Example 2 of the present disclosure;

[0041] Figure 10 Shows the 1H NMR spectrum of the palladium complex Pd1 in Example 1 of the present disclosure; and

[0042] Figure 11 The carbon-13 nuclear magnetic resonance spectrum of the palladium complex Pd1 in Embodiment 1 of the present disclosure is shown. Detailed implementation manners

[0043] In related technologies, neutral nickel complexes based on salicylaldimine ligands are mostly used. Such neutral nickel complexes can synthesize polyolefins with relatively excellent high molecular weights, but the molecular weights of the polyolefins synthesized by them have been limited to several thousand. In the process of implementing the present disclosure, it is found that introducing groups with methoxy, hydroxyl or sodium oxy substituents into the α-diimine backbone can synergistically construct a relatively large steric hindrance effect, thereby controlling the spatial range of subsequent metal-nitrogen coordination.

[0044] In view of this, the present disclosure introduces methoxy, hydroxyl or sodium oxy substituents into the α-diimine system. Through the synergistic effect of the α-diimine and the methoxy, hydroxyl or sodium oxy substituents, a relatively large steric hindrance range is constructed, reducing the uncontrolled chain walking and chain transfer behaviors of metal groups when subsequent metal complexes are formed, thereby improving the selectivity and yield during metal coordination, reducing the degree of branching of the polymers prepared subsequently, and increasing the molecular weight of the polyolefin formed during catalytic polymerization.

[0045] To make the objectives, technical solutions and advantages of the present disclosure clearer and more understandable, the following further describes the present disclosure in detail with reference to specific embodiments and the accompanying drawings.

[0046] According to an embodiment of one aspect of the present disclosure, an α-diimine ligand compound of Formula I is provided, wherein R1, R2, R3, and R4 are each independently selected from any one of C1-C 11 alkyl, substituted or unsubstituted benzhydryl, and hydrogen; R5 is selected from any one of methoxy, hydroxyl or sodium oxy substituents; wherein when there is a substituent on the benzhydryl, the substituent is selected from C1-C 11 alkyl, C1-C 11 alkoxy, and C2-C 11 alkenyl.

[0047]

[0048] In the embodiment of the present disclosure, for the ligand compound shown in Formula I, the α-diimine backbone and the methoxy, hydroxyl or sodium oxy substituents of the R5 group form a relatively large steric hindrance space. Thus, when subsequent metal coordination occurs, the space where the metal group can coordinate during insertion is relatively small, and the rotation of the N-aryl part at high temperatures is inhibited. Due to the limitation of space, the subsequent chain walking behavior of the metal group is further inhibited, thereby reducing the degree of branching during subsequent catalytic coordination polymerization of olefin monomers, which is beneficial to making the olefin polymers prepared subsequently have less degree of branching and higher molecular weights.

[0049] Furthermore, the R5 group can be a sodium oxy substituent. When the R5 group is a sodium oxy substituent, the two sodium oxy substituents contain two oxygen atoms, both of which can form hydrogen bond interactions with the hydroxyl groups on the surface of the carrier during subsequent loading, that is, ionic anchoring is formed. When forming the supported catalyst subsequently, through the ionic anchoring between the sodium oxy substituent group and the carrier, it is beneficial to increase the number of active sites on the surface of the subsequent carrier and form a more sufficient and stable loading structure, which is conducive to achieving a higher molecular weight of the olefin polymer, thereby achieving a better polymerization effect.

[0050] In the α-diimine metal complex provided by the embodiment of the present disclosure, the metal Lewis acid will coordinate with the N atom in the catalyst ligand.

[0051] In the embodiments of the present disclosure, R1, R2, R3, and R4 are each independently selected from one of the following structures:

[0052]

[0053] In the process of conducting the related preliminary experiments of the present disclosure, it was found that when R1, R2, R3, and R4 are selected from the above groups, the degree of branching of the subsequent prepared olefin polymer is lower and the molecular weight is higher.

[0054] In some embodiments of the present disclosure, the α-diimine ligand compound includes compounds of formulas I1 to I 12 shown in the structure:

[0055]

[0056]

[0057] According to the embodiments of the present disclosure, a method for preparing the ligand compound of the α-diimine of formula I is also provided. When R5 is a methoxy group or a hydroxyl group, the preparation methods are basically the same. For the sake of illustration, taking R5 as a hydroxyl group as an example, the following preparation process is specifically described:

[0058] Dissolve 10 mmol of the compound shown in formula A, 10 mmol of the compound shown in formula B, and 10 mmol of 2,3-butanedione in the first organic solvent, add 1 mL of formic acid dropwise, and stir well. Then reflux and react at 70 - 90 °C for 6 - 16 hours. After the reaction is completed, separate the precipitated yellow solid, wash it with an organic solvent, and vacuum dry it overnight at 50 °C to finally obtain the ligand compound when R5 is a hydroxyl group.

[0059]

[0060] The reaction change process is as follows:

[0061]

[0062] In some embodiments of the present disclosure, the reaction conditions for preparing the ligand compound when R5 is a hydroxyl group or a methoxy group are as follows: under the condition of 70-90 °C, for example, it can be 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, preferably 80 °C; the reaction is carried out for 6-16 h, for example, it can be 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, preferably 12 h.

[0063] In some embodiments of the present disclosure, the first organic solvent includes at least one of methanol, tetrahydrofuran, N,N-dimethylformamide, toluene, and dichloromethane.

[0064] In some embodiments of the present disclosure, formic acid is used as the catalyst for the reaction. During the catalytic process, formic acid first forms an intermediate with 2,3-butanedione, and then further reacts with the amino group, so that the compounds shown in Formula A and the compounds shown in Formula B are more likely to react, further promoting the forward reaction.

[0065] When R5 is a sodium oxygen substituent, the same parts of its preparation process as the above preparation method will not be described herein again. The difference is that after preparing the ligand compound when R5 is a hydroxyl group, under anhydrous and anaerobic conditions, the ligand compound when R5 is a hydroxyl group is dissolved in anhydrous first organic solvent, and sodium hydride is added and reacted at 5-25 °C for 1-3 h. After the reaction is completed, recrystallization and drying are carried out in sequence to obtain the ligand compound when R5 is a sodium oxygen substituent.

[0066] The reaction change process is as follows:

[0067]

[0068] In some embodiments of the present disclosure, the molar ratio of the ligand compound when R5 is a hydroxyl group to sodium hydride is 1:2.

[0069] Furthermore, the present disclosure also provides a method for preparing the compound shown in Formula A, including:

[0070] Mix 10.1 mmol of the compound shown in Formula C and 10 mmol of 2-methoxyaniline and carry out a heating reaction at a temperature of 120 °C, then add a hydrochloric acid solution of zinc chloride and further raise the temperature to 160 °C. After reacting for 30 min, cool to 5-25 °C, and then add ethyl acetate to dissolve to obtain the compound shown in Formula E.

[0071]

[0072] The reaction change process is as follows:

[0073]

[0074] Mix 10 mmol of the compound represented by Formula E prepared and 10.1 mmol of the compound represented by Formula D, and repeat the above reaction steps to finally prepare the compound represented by Formula A.

[0075] R1—OH

[0076] Formula D

[0077] The reaction change process is as follows:

[0078]

[0079] According to an embodiment of the present disclosure, the preparation method of the compound represented by Formula B is basically the same as that of Formula A, and will not be elaborated here.

[0080] According to an embodiment of the present disclosure, an α-diimine metal complex of Formula II is further provided, M includes any one of nickel and palladium; X includes at least one of methyl, chlorine or bromine; R1, R2, R3, and R4 are each independently selected from C1-C 11 alkyl, substituted or unsubstituted diphenylmethyl, hydrogen; R5 is selected from any one of methoxy, hydroxyl or sodium oxygen substituent, wherein when there is a substituent on the diphenylmethyl, the substituent is selected from C1-C 11 alkyl, C1-C 11 alkoxy, C2-C 11 alkenyl.

[0081]

[0082] In some embodiments of the present disclosure, the definitions of R1, R2, R3 and R4 in Formula II are as described above, and will not be elaborated here.

[0083] According to an embodiment of the present disclosure, the insertion position of the metal coordination center in the formed complex has a good regulation effect on the catalytic polymerization of olefin monomers. By constructing an adapted steric space, the space of the metal insertion position can be relatively restricted, thereby inhibiting the uncontrolled chain walking reaction of the metal group, further improving the selectivity and yield of the reaction, preventing the occurrence of unnecessary side reactions, and improving the controllability of the reaction.

[0084] In some embodiments of the present disclosure, the above α-diimine metal complex includes compounds having the structures shown in Formula II1 to Formula II 10 as follows:

[0085]

[0086]

[0087] According to an embodiment of the present disclosure, a method for preparing an α-diimine metal complex of formula II is further provided.

[0088] In some embodiments of the present disclosure, the specific preparation steps may include: under anhydrous and anaerobic conditions, 1 mmol of the compound shown in formula I and 1 mmol of CODMMeX or 1 mmol of DMEMX2 are added to a first organic solvent and mixed and stirred. Then, for example, CODPdMeCl or DMENiBr2 can be added as needed. DMENiBr2 is successively dried, washed, filtered, and dried to prepare an α-diimine metal complex shown in formula II. The reaction change process is as follows:

[0089]

[0090] According to an embodiment of the present disclosure, an α-diimine metal-supported catalyst is further provided, which includes the metal complex and a support as described above, wherein the metal complex is supported on the support. When the R5 group is an oxygen-sodium substituent, two oxygen atoms in the two oxygen-sodium substituents can form a hydrogen bond with the hydroxyl groups on the surface of the support, thereby strengthening the interaction between the α-diimine metal-supported catalyst and the support, increasing the number of active sites on the surface of the support, and forming an ion-anchoring effect. This ion-anchoring effect can strengthen the interaction between the α-diimine metal-supported catalyst and the support through electrostatic and coordination effects, thereby enhancing the active sites of the catalyst.

[0091] In some embodiments of the present disclosure, the support includes at least one of silica, magnesium chloride, or aluminum oxide. Preferably, the support is silica.

[0092] According to an embodiment of the present disclosure, a method for preparing an α-diimine metal-supported catalyst is further provided, including: adding the α-diimine metal complex of formula II and the support to a first organic solvent and stirring for 8 to 16 h, and then successively filtering and drying to obtain the α-diimine metal-supported catalyst.

[0093] According to an embodiment of the present disclosure, an application of a supported catalyst in catalyzing the polymerization reaction of C2-C 11 olefin monomers is further provided.

[0094] In some embodiments of the present disclosure, catalyzing the polymerization reaction of C2-C 11 olefin monomers includes:

[0095] Adding a cocatalyst and C2-C 11 olefin monomers to an organic solvent, and then injecting the supported catalyst, such that C2-C 11to carry out a coordination polymerization reaction on an olefin monomer.

[0096] In some embodiments of the present disclosure, the polymerization reaction includes homopolymerization and / or copolymerization of C2-C 11 olefin monomers.

[0097] Specifically, when the polymerization reaction is a homopolymerization reaction of C2-C4 olefin monomers, a C2-C4 olefin monomer, a cocatalyst, and a second organic solvent are added to a reaction vessel and mixed evenly, and an α-diimine metal-supported catalyst containing a methoxy, hydroxyl, or sodium oxy substituent is added. Under the condition of 1-50 atmospheres, a homopolymerization reaction is carried out, and quenching is carried out after the reaction ends.

[0098] When the polymerization reaction is homopolymerization of long-chain olefins with more than C5, other conditions are the same as those of the above homopolymerization reaction. The difference is that when homopolymerizing long-chain olefins, it needs to be carried out under an inert gas atmosphere.

[0099] When the polymerization reaction is a copolymerization reaction of C2-C4 olefin monomers, a copolymer monomer of C2-C4 olefins, a cocatalyst, and a second organic solvent are added to a reaction vessel and mixed evenly, and an α-diimine metal-supported catalyst containing a methoxy, hydroxyl, or sodium oxy substituent is added. Under the condition of 1-50 atmospheres, a homopolymerization reaction is carried out, and quenching is carried out after the reaction ends.

[0100] In some embodiments of the present disclosure, the second organic solvent includes at least one of toluene, benzene, and n-heptane. It should be noted that the second organic solvent and the first organic solvent can be the same; the cocatalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum, an alkali metal, or an alkali metal salt, where the alkali metal can be, for example, lithium, sodium, or potassium; C2-C 11 olefin monomers include at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene, and 1-octene. During the screening process of the organic solvent, the cocatalyst, and the olefin monomer, it is found that when the organic solvent, the cocatalyst, and the olefin monomer are respectively selected from the above specific compounds, the resulting polymerization product has a higher molecular weight, stronger activity, and lower degree of branching.

[0101] When the metal is nickel, the specific preparation steps are as follows:

[0102] 500 eq of diethylaluminum chloride (AlEt2Cl) was mixed with 18 mL of n-hexane in a pressure vessel and stirred evenly with a magnetic stir bar. Then the pressure vessel was connected to a high-pressure pipeline, and the solution was degassed. The vessel was heated to 30 °C using an oil bath and the pressure valve was adjusted to 1 atm. 2 μmol of α-diimine nickel-supported catalyst in 2 mL of CH2Cl2 was injected into the polymerization system through a syringe. Under rapid stirring, the reactor was pressurized and maintained at 8.0 atm of ethylene. After 30 min, the pressure vessel was vented and the resulting crude olefin polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 h to obtain the olefin polymer.

[0103] When the metal is palladium, the specific preparation steps are as follows:

[0104] 1.2 eq of sodium borate salt (NaBAF) was mixed with 18 mL of n-hexane in a pressure vessel and stirred evenly with a magnetic stir bar. Then the pressure vessel was connected to a high-pressure pipeline, and the solution was degassed. The vessel was heated to 20 - 80 °C using an oil bath and the pressure valve was adjusted to 1 atm. 10 μmol of α-diimine palladium-supported catalyst in 2 mL of CH2Cl2 was injected into the polymerization system through a syringe. Under rapid stirring, the reactor was pressurized and maintained at 8.0 atm of ethylene. After 60 min, the pressure vessel was vented and the resulting crude olefin polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 h to obtain the olefin polymer.

[0105] When using methyl undecylenate or 6-chloro-1-hexene for copolymerization reaction, the specific preparation steps are as follows:

[0106] 500 eq of diethylaluminum chloride (AlEt2Cl), n-hexane and methyl undecylenate or 6-chloro-1-hexene with a total volume of 18 mL were added to a pressure vessel and mixed evenly with a magnetic stir bar. The pressure vessel was connected to a high-pressure pipeline, and the solution was degassed. At the same time, the vessel was heated to 20 - 80 °C using an oil bath and the pressure valve was adjusted to 1 atm. 10 μmol of α-diimine nickel-supported catalyst dissolved in 2 mL of dichloromethane was injected into the polymerization system through a syringe. Under rapid stirring, the reactor was pressurized and maintained at 8.0 atm of ethylene. After 30 min, the pressure vessel was vented and the resulting crude olefin polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 h to obtain the olefin polymer.

[0107] When using methyl acrylate for copolymerization reaction, the specific preparation steps are as follows:

[0108] 500 eq of diethylaluminum chloride, n-hexane and methyl acrylate with a total volume of 18 mL were added to a pressure vessel and mixed, and stirred evenly with a magnetic stir bar. The pressure vessel was connected to a high-pressure pipeline, and the solution was degassed. At the same time, the vessel was heated to 20-80 °C using an oil bath and the pressure valve was adjusted to 1 atmosphere. 20 μmol of α-diimine palladium-supported catalyst dissolved in 2 mL of dichloromethane was injected into the polymerization system through a syringe. Under rapid stirring, the reactor was pressurized and maintained at 8.0 atm of ethylene. After 120 min, the pressure vessel was vented and the resulting crude olefin polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried in a vacuum environment at 50 °C for 24 hours to obtain the olefin polymer.

[0109] Embodiments of the present disclosure provide a class of α-diimine ligand compounds containing methoxy, hydroxyl or sodium oxy substituents, their metal complexes, α-diimine metal-supported catalysts and their applications. Different functional group substituents of the α-diimine metal complexes have relatively distinct activity contrasts, and show higher stability and activity after loading. In particular, when this supported catalyst is applied to homogeneous catalytic polymerization, the α-diimine nickel / palladium-supported catalyst containing methoxy substituents shows relatively better homopolymerization effect and higher tolerance to polar monomers; when this supported catalyst is applied to heterogeneous catalytic polymerization, the α-diimine nickel / palladium catalyst containing sodium oxy substituents shows relatively better homopolymerization effect. The main reasons are that during homogeneous polymerization, the steric hindrance of the methoxy group is the largest, so it will increase the axial steric hindrance of the metal center to a greater extent and is more likely to inhibit β-H elimination; under heterogeneous polymerization conditions, the oxygen atom on the sodium oxy group and the hydrogen atom on the support can form a strong hydrogen bond, so the catalyst can contact the support more closely and achieve a better loading effect.

[0110] The present disclosure will be further illustrated by the following examples. In the following detailed description, for the sake of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, obviously, one or more embodiments can also be implemented without these specific details. Moreover, without conflict, the details in the following embodiments can be combined arbitrarily into other feasible embodiments.

[0111] It should be noted that the following examples illustrate the specific content of the present disclosure. The data given include the synthesis of ligands, the synthesis of metal compounds, and the methods of ethylene polymerization or copolymerization. Among them, the synthesis of complexes and the polymerization process are carried out under anhydrous and anaerobic conditions. All sensitive substances are stored in a glove box. All solvents are strictly dried to remove water, and ethylene gas is purified through a column for removing water and oxygen. Without special instructions, all raw materials are used directly after being purchased. The methods used in the following examples, such as column chromatography, are well-known methods in the art and can be carried out according to the descriptions in textbooks or relevant literature, and will not be elaborated here.

[0112] The nuclear magnetic resonance (NMR) detection in the examples of the present disclosure uses a Bruker 400 MHz NMR instrument. Elemental analysis is determined by the Physical and Chemical Analysis Center of the University of Science and Technology of China. Molecular weight and molecular weight distribution are determined by high-temperature and / or room-temperature gel permeation chromatography (GPC). Mass spectrometry is determined using a Thermo LTQ Orbitrap XL.

[0113] Example 1

[0114] Synthesis of 2,4-dibenzoyl-6-methoxyaniline

[0115]

[0116] 10.00 mmol of 2-methoxyaniline and 20.00 mmol of diphenylmethanol were placed in a pressure-resistant bottle and mixed, and then heated to 120 °C. Subsequently, a hydrochloric acid solution of zinc chloride was rapidly added to the mixture, and it was observed that the reaction exothermed rapidly and foamed. Then the reaction temperature was raised to 160 °C. After reacting for 30 minutes, the heater was turned off, and the reaction kettle was allowed to cool naturally to 20 °C. Then 200 mL of ethyl acetate was added to dissolve. The obtained ethyl acetate layer was washed 3 times with an aqueous solution of sodium bicarbonate and then dried with anhydrous sodium sulfate. Separation was carried out by column chromatography to prepare white solid 2,4-dibenzoyl-6-methoxyaniline, and the reaction yield was 85%. Figure 1 The proton nuclear magnetic resonance (¹H NMR) spectrum of 2,4-dibenzoyl-6-methoxyaniline in Example 1 is shown, as Figure 1 shown, and the structure of the prepared product can be determined. 1 ¹H NMR (400 MHz, Chloroform-d) δ 7.31–7.26 (m, 5H), 7.26–7.17 (m, 7H), 7.09 (dd, J = 15.2, 7.5 Hz, 8H), 6.57 (s, 1H), 6.13 (s, 1H), 5.54 (s, 1H), 5.39 (s, 1H), 3.76 (s, 3H), 3.55 (d, J = 22.2 Hz, 2H). Figure 2 The carbon nuclear magnetic resonance (¹³C NMR) spectrum of 2,4-dibenzoyl-6-methoxyaniline in Example 1 of the present disclosure is shown,Figure 3 The mass spectrum of 2,4-dibenzoyl-6-methoxyaniline in Example 1 is shown. As Figure 2 , Figure 3 shown, its structure can be determined again. 13 C NMR (101 MHz, Chloroform-d) δ 144.58, 142.42, 129.41, 129.27, 128.43, 128.08, 126.50, 125.98, 123.53, 109.83, 56.50, 55.59, 52.21.

[0117] Synthesis of Complex 1

[0118]

[0119] After dissolving 10.00 mmol of the obtained 2,4-dibenzoyl-6-methoxyaniline and 10.00 mmol of 2,3-butanedione in 30 mL of methanol solution, 1 mL of formic acid was added dropwise. After stirring well, the mixture was refluxed at 80 °C for 12 hours. After the reaction, a yellow solid precipitated in the solution. The yellow solid obtained by filtration was washed 3 times with 20 mL of methanol and vacuum dried overnight at 50 °C to obtain Complex 1, which is (2E,3E)-N2,N3-bis(2,4-dibenzoyl-6-methoxyphenyl)butane-2,3-diamine, and its reaction yield was 80%. Figure 4 The 1H NMR spectrum of Complex 1 in Example 1 is shown. As Figure 4 shown, the structure of the prepared product can be determined. 1 1H NMR (400 MHz, Chloroform-d) δ 7.16–7.05 (m, 24H), 6.98–6.86 (m, 16H), 6.44 (d, J = 1.9 Hz, 1H), 6.27 (d, J = 1.7 Hz, 1H), 6.00 (d, J = 1.9 Hz, 1H), 5.45 (s, 1H), 5.39 (s, 1H), 5.34 (s, 1H), 5.25 (s, 1H), 3.63 (s, 3H), 3.52 (s, 3H), 2.41 (s, 3H), 1.17 (s, 3H). Figure 5 The 13C NMR spectrum of Complex 1 in Example 1 is shown. As Figure 5 shown, its structure can be determined again. 1313C NMR (101 MHz, Chloroform-d) δ 144.45, 143.94, 142.63, 142.29, 135.13, 129.35, 129.29, 129.23, 129.21, 128.37, 128.16, 128.11, 128.03, 126.45, 126.19, 125.93, 123.49, 123.21, 110.66, 109.80, 56.58, 56.43, 55.56, 55.46, 52.39, 52.08, 24.80, 14.58。

[0120] Synthesis of Nickel Complex Ni1

[0121]

[0122] In a glove box under a nitrogen atmosphere, 1.00 mmol of Complex 1 was dissolved in 20 mL of dichloromethane, and 1.00 mmol of (DME)NiBr2 was added. The mixture was stirred at room temperature for 12 h. After the reaction was completed, the mixture was first passed through diatomaceous earth, and then the filtrate was dried. Then, 30 mL of dry n-hexane was added to the flask to wash the residue, and the solid was collected by filtration and then dried to obtain the nickel complex Ni1 as a dark red solid. Figure 8 The mass spectrum of the nickel complex Ni1 in Example 1 of the present invention is shown, as Figure 8 shown, and the structure of the nickel complex Ni1 can be confirmed. MALDI-TOF (m / z): Calcd for C70H60BrN2NiO2: 1099.8594; Found: [M-Br]+: 1099.4086. Anal. Calcd. for C70H60Br2N2NiO2: C, 71.27; H, 5.13; N, 2.37. Found: C, 71.29; H, 5.16; N, 2.38.

[0123] Synthesis of Palladium Complex Pd1

[0124]

[0125] In a glove box under a nitrogen atmosphere, 1.00 mmol of Complex 1 and 1.00 mmol of (COD)PdMeCl were dissolved in 20 mL of dichloromethane, and the mixture was stirred at 20 °C for 12 h. After the reaction was completed, the solvent was dried, and then 30 mL of dry n-hexane was added to the flask to wash the residue. The solid was collected by filtration and then dried to obtain the palladium complex Pd1 as an orange solid. Figure 10 The 1H NMR spectrum of the palladium complex Pd1 in Example 1 of the present disclosure is shown, as Figure 10The structure of the palladium complex Pd1 can be confirmed as shown. 1 H NMR (400 MHz, Chloroform-d) δ 7.28 (d, J = 7.5 Hz, 2H), 7.18 (dd, J = 8.3, 5.5 Hz, 7H), 7.15–6.92 (m, 31H), 6.60 (s, 1H), 6.52 (s, 1H), 6.37 (s, 2H), 6.29 (s, 1H), 5.96 (s, 1H), 5.39 (d, J = 8.7 Hz, 2H), 3.72 (d, J = 12.3 Hz, 6H), 0.69 (s, 3H), 0.52 (s, 3H), 0.46 (s, 3H). Figure 11 The carbon nuclear magnetic resonance spectrum of the palladium complex Pd1 in Example 1 of the present disclosure is shown, as Figure 11 shown, and the structure can be confirmed again. 13 C NMR (101 MHz, Chloroform-d) δ 171.45, 148.59, 143.17, 142.78, 142.61, 142.45, 142.02, 141.01, 140.53, 139.89, 136.87, 136.11, 129.92, 129.60, 128.77, 128.43, 128.37, 128.23, 128.19, 127.44, 127.28, 127.15, 127.13, 127.05, 126.97, 126.73, 125.38, 125.34, 125.14, 124.93, 124.89, 121.81, 121.78, 110.03, 109.78, 55.58, 55.28, 55.08, 51.39, 51.04, 17.60, 16.66.

[0126] Example 2

[0127] Synthesis of 2-Amino-3,5-dibenzoylphenol

[0128]

[0129] 10.00 mmol of 2-aminophenol and 20.00 mmol of diphenylmethanol were placed in a pressure-resistant flask and mixed, and then heated to a temperature of 120 °C. Then, a hydrochloric acid solution of zinc chloride was quickly added to the mixture, and it was observed that the reaction rapidly exothermed and foamed. Then the reaction temperature was raised to 160 °C. After reacting for 30 minutes, the heater was turned off. After the reaction kettle was naturally cooled to 20 °C, 200 mL of ethyl acetate was added to dissolve it. The obtained ethyl acetate layer was washed 3 times with an aqueous sodium bicarbonate solution and then dried with anhydrous sodium sulfate. Separation was carried out by column chromatography to prepare the white solid 2-amino-3,5-dibenzoyl phenol, and its reaction yield was 80%.

[0130] Synthesis of Complex 2

[0131]

[0132] The obtained 10.00 mmol of 2-amino-3,5-dibenzoyl phenol and 10.00 mmol of 2,3-butanedione were dissolved in 30 mL of a methanol solution, 1 mL of formic acid was added dropwise, and after sufficient stirring, the mixture was refluxed at a temperature of 80 °C for 12 hours. After the reaction was completed, a yellow solid precipitated in the solution. The yellow solid obtained by filtration separation was washed 3 times with 20 mL of methanol and vacuum dried overnight at a temperature of 50 °C to obtain Complex 2, that is, (2,2'-butane-2,3-diylidenebis(azanediyl))bis(3,5-dibenzoyl phenol), and its reaction yield was 78%. Figure 6 The 1H NMR spectrum of Complex 2 in Example 2 is shown, as Figure 6 shown, the structure of the prepared product can be determined. 1 H NMR (400 MHz, Chloroform-d) δ 7.23–7.09 (m, 23H), 7.09–6.89 (m, 17H), 6.42 (s, 2H), 6.02 (s, 2H), 5.37 (s, 2H), 5.22 (s, 2H), 4.15 (s, 2H), 1.05 (s, 6H). Figure 7 The 13C NMR spectrum of Complex 2 in Example 2 is shown, as Figure 7 shown, its structure can be determined again. 1313C NMR (101 MHz, Chloroform-d) δ 144.38, 144.33, 142.15, 141.84, 134.63, 129.40, 129.27, 129.13, 128.49, 128.37, 128.23, 128.00, 127.98, 126.62, 126.57, 125.87, 125.85, 124.84, 123.78, 116.82, 81.50, 56.20, 52.01, 21.32。

[0133] Synthesis of Complex 3

[0134]

[0135] Under nitrogen protection, 10.00 mmol of (2,2'-butane-2,3-diylbis(azanediyl))bis(3,5-dibenzoylphenol) was dissolved in 30 mL of dry tetrahydrofuran, placed in an ice-water bath at -10 °C, and 20.00 mmol of sodium hydride was added and reacted for 1 hour. Then, the solvent was dried under reduced pressure at 20 °C to obtain Complex 3, which is 2,2'-butane-2,3-diylbis(azanediyl)bis(azanediyl)bis(3,5-dibenzoylphenolate sodium).

[0136] Synthesis of Nickel Complex Ni2

[0137]

[0138] In a glove box under a nitrogen atmosphere, 1.00 mmol of Complex 2 was dissolved in 20 mL of dichloromethane. After adding 1.00 mmol of (DME)NiBr2, the mixture was stirred at 20 °C for 12 h. After the reaction was completed, the mixture was first passed through diatomaceous earth, then the filtrate was dried under reduced pressure. Then, 30 mL of dry n-hexane was added to the flask to wash the residue, and the solid was collected by filtration and then dried under reduced pressure to obtain the red solid nickel complex Ni2.

[0139] Synthesis of Nickel Complex Ni3

[0140]

[0141] In a glove box under a nitrogen atmosphere, 1.00 mmol of Complex 3 was dissolved in 20 mL of dichloromethane. 1.00 mmol of (DME)NiBr2 was added, and the mixture was stirred at 20 °C for 12 h. After the reaction was completed, the mixture was first passed through diatomaceous earth, then the filtrate was dried under reduced pressure. Then, 30 mL of dry n-hexane was added to the flask, and the residue was washed. The solid was collected by filtration and then dried under reduced pressure to obtain the black-red solid nickel complex Ni3. Figure 9The mass spectrum of the nickel complex Ni3 in Embodiment 2 of the present disclosure is shown. As Figure 9 shown, the structure of the nickel complex Ni3 can be confirmed. MALDI-TOF (m / z): Calcd for C 68 H 54 N2NiO2: 989.8854; Found: [M - 2Br - 2Na] + : 990.4936. Anal. Calcd. for C 68 H 54 Br2N2Na2NiO2: C, 68.31; H, 4.55; N, 2.34. Found: C, 68.29; H, 4.57; N, 2.37.

[0142] Synthesis of Palladium Complex Pd2

[0143]

[0144] In a glove box under a nitrogen atmosphere, 1.00 mmol of Complex 2 and 1.00 mmol of (COD)PdMeCl were dissolved in 20 mL of dichloromethane, and the mixture was stirred at 20 °C for 12 h. After the reaction was completed, the solvent was first evaporated, and then 30 mL of dry n-hexane was added to the flask to wash the residue. The solid was collected by filtration and then dried to obtain the red solid palladium complex Pd2.

[0145] Synthesis of Palladium Complex Pd3

[0146]

[0147] In a glove box under a nitrogen atmosphere, 1.00 mmol of Complex 3 and 1.00 mmol of (COD)PdMeCl were dissolved in 20 mL of dichloromethane, and the mixture was stirred at 20 °C for 12 h. After the reaction was completed, the solvent was first evaporated, and then 30 mL of dry n-hexane was added to the flask to wash the residue. The solid was collected by filtration and then dried to obtain the black-red solid palladium complex Pd3.

[0148] Example 3

[0149] 2 μmol of the nickel complex Ni2 prepared in Example 2, 100 mg of silica, and 15 mL of dichloromethane were stirred in a glove box at 20 °C for 12 h, and the filtrate was filtered and dried to obtain the light yellow solid Ni2@SiO2.

[0150] Example 4

[0151] 2 μmol of the palladium complex Pd2 prepared in Example 2, 100 mg of silica, and 15 ml of dichloromethane were stirred in a glove box at 20 °C for 12 h. The residue was filtered and dried to obtain a light yellow solid Pd2@SiO2.

[0152] Example 5

[0153] 2 μmol of the palladium complex Pd3 prepared in Example 2, 100 mg of silica, and 15 ml of dichloromethane were stirred in a glove box at 20 °C for 12 h. The residue was filtered and dried to obtain a light yellow solid Pd3@SiO2.

[0154] Example 6

[0155] 3 μmol of the nickel complex Ni3 prepared in Example 2, 100 mg of silica, and 15 ml of dichloromethane were stirred in a glove box at 20 °C for 12 h. The residue was filtered and dried to obtain a light red solid Ni3@SiO2.

[0156] Example 7

[0157] 1 μmol of the palladium complex Pd2 prepared in Example 2, 100 mg of silica, and 15 ml of dichloromethane were stirred in a glove box at 20 °C for 12 h. The residue was filtered and dried to obtain a light orange solid Pd2@SiO2.

[0158] Example 8

[0159] 2 μmol of the palladium complex Pd3 prepared in Example 2, 100 mg of silica, and 15 ml of dichloromethane were stirred in a glove box at 20 °C for 12 h. The residue was filtered and dried to obtain a red solid Pd3@SiO2.

[0160] The catalytic ethylene homopolymerization reaction effects of the α-diimine nickel / palladium catalysts with methoxy, hydroxyl, and sodium oxy substituents before and after loading prepared in the above Examples 1-8 were tested.

[0161] In a typical experiment, 500 eq of AlEt2Cl, 18 mL of n-hexane, and a magnetic stir bar were charged into a 350 mL thick-walled glass pressure vessel in a glove box. The pressure vessel was connected to a high-pressure pipeline and the solution was degassed. The vessel was heated to 20 °C, 50 °C, and 80 °C using an oil bath and equilibrated for 15 minutes. 2 μmol of the α-diimine nickel catalyst with methoxy, hydroxy, and sodium oxy substituents before and after loading obtained in Examples 1-8 above in 2 mL of CH2Cl2 was injected into the polymerization system by syringe. Under rapid stirring, the reactor was pressurized and maintained at 8.0 atm of ethylene. After 30 min, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 h.

[0162] In another typical experiment, 1.2 eq of NaBAF, 18 mL of n-hexane, and a magnetic stir bar were charged into a 350 mL thick-walled glass pressure vessel in a glove box. The pressure vessel was connected to a high-pressure pipeline and the solution was degassed. The vessel was heated to 20 °C, 50 °C, and 80 °C using an oil bath and equilibrated for 15 minutes. 10 μmol of the α-diimine palladium catalyst with methoxy, hydroxy, and sodium oxy substituents before and after loading obtained in Examples 1-8 above in 2 mL of CH2Cl2 was injected into the polymerization system by syringe. Under rapid stirring, the reactor was pressurized and maintained at 8.0 atm of ethylene. After 1 h, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1) and dried under vacuum at 50 °C for 24 h.

[0163] The relevant data for the catalytic ethylene homopolymerization obtained are shown in Table 1 below.

[0164] Table 1 Ethylene Homopolymerization Table a

[0165]

[0166] a Polymerization conditions: Ni:AlEt2Cl (500 equivalents), 8 atm ethylene pressure, 30 min; Pd:NaBAF (1.2 equivalents), 8 atm ethylene pressure, 1 h. b Activity is in units of 10 5 g.mol -1 .h -1 as the unit. c Molecular weight is in units of 10 4 g.mol -1. in units. Ni: determined by gel permeation chromatography (GPC) using polystyrene standards in trichlorobenzene at 150 °C; Pd: determined by gel permeation chromatography (GPC) using polystyrene standards in tetrahydrofuran. d The degree of branching is given per 1000 carbon atoms. Number of branches per 1000C = (CH3 / 3) / [(CH + CH2 + CH3) / 2] * 1000. e Determined by differential scanning calorimetry (DSC, second heating).

[0167] The catalytic ethylene copolymerization reaction effect of the α-diimine nickel / palladium catalysts with methoxy, hydroxyl, and sodium oxy substituents before and after loading prepared in the above Examples 1-8 was tested.

[0168] Methyl undecenoate or 6-chloro-1-hexene copolymerization reaction

[0169] In a glove box, a total of 18 mL of 500 eq of diethylaluminum chloride, n-hexane, and methyl undecenoate or 6-chloro-1-hexene, and a magnetic stir bar were added to a 350 mL thick-walled glass pressure vessel. The pressure vessel was connected to a high-pressure pipeline and the vessel was degassed while heating the vessel to 30 °C using an oil bath, and then the pressure valve was adjusted to 1 atmosphere. 10 μmol of nickel complex Ni1 and 10 μmol of nickel complex Ni3 catalysts dissolved in 2 mL of dichloromethane were respectively injected into the polymerization system through a syringe. Under rapid stirring, the reactor was pressurized to 8 atmospheres to start the polymerization. After 30 minutes, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1), and then dried in a vacuum drying oven at 50 °C for 24 h.

[0170] Methyl acrylate copolymerization reaction

[0171] In a glove box, a total of 18 mL of 1.2 eq of sodium borate salt, n-hexane, and methyl acrylate, and a magnetic stir bar were added to a 350 mL thick-walled glass pressure vessel. The pressure vessel was connected to a high-pressure pipeline and the vessel was degassed while heating the vessel to 30 °C using an oil bath, and then the pressure valve was adjusted to 1 atmosphere. 20 μmol of palladium complex Pd1 and 20 μmol of nickel complex Pd3 catalysts dissolved in 2 mL of dichloromethane were respectively injected into the polymerization system through a syringe. Under rapid stirring, the reactor was pressurized to 8 atmospheres to start the polymerization. After 120 min, the pressure vessel was vented and the polymer was precipitated in acidified methanol (methanol / HCl = 50 / 1), and then dried in a vacuum drying oven at 50 °C for 24 h.

[0172] The relevant data of the obtained catalytic ethylene copolymerization reaction are shown in Table 2 below.

[0173] Table 2 Ethylene Copolymerization Table a

[0174]

[0175] a Polymerization conditions: 30 °C, Ni: 8 atm ethylene pressure, 30 min; Pd: 8 atm ethylene pressure, 2 h. b The activity unit is 10 4 g.mol -1 .h -1 . c Determined by 1 H NMR. d The molecular weight is in units of 10 4 g.mol -1 . Ni: Measured by gel permeation chromatography (GPC) with polystyrene standards in trichlorobenzene at 150 °C; Pd: Measured by gel permeation chromatography (GPC) with polystyrene standards in tetrahydrofuran. e is measured by differential scanning calorimetry (DSC, second heating).

[0176] The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present disclosure. It should be understood that the above are only specific embodiments of the present disclosure and are not used to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present disclosure shall be included within the protection scope of the present disclosure.

Claims

1. An α-diimine ligand compound having the structural formula shown in formula (I): Formula (I) R1, R2, R3, and R4 are each independently a substituted or unsubstituted benzhydryl; R5 is selected from any one of a methoxy group, a hydroxyl group or a sodium oxy substituent; wherein, When there is a substituent on the benzhydryl, the substituent is selected from any one of alkyl groups having C1 to C 11 , alkoxy groups having C1 to C 11 , and alkenyl groups having C2 to C 11 .

2. The ligand compound according to claim 1, wherein, R1, R2, R3, and R4 are each independently selected from one of the following structures: 。 3. The ligand compound according to claim 1, wherein The ligand compound has the structure shown in any one of formula (I1), formula (I5), and formula (I9): Formula (I1) Formula (I5) Formula (I9).

4. An α-diimine metal complex having the structural formula shown in formula (II): Formula (II) Among them, M includes any one of nickel and palladium; X includes at least one of methyl, chlorine, and bromine; R1, R2, R3, and R4 are each independently a substituted or unsubstituted benzhydryl; R5 is selected from any one of methoxy, hydroxy, and sodium oxide substituents; Among them, when there is a substituent on the benzhydryl, the substituent is selected from any one of C1-C 11 alkyl, C1-C 11 alkoxy, C2-C 11 alkenyl.

5. An α-diimine metal-supported catalyst, comprising the metal complex described in claim 4 and a support, wherein, The metal complex is supported on a carrier.

6. The supported catalyst according to claim 5, wherein, The carrier includes at least one of silica, magnesium chloride, and aluminum oxide.

7. Use of a supported catalyst as described in claim 5 or 6 in the polymerization reaction of C2-C 11 olefin monomers.

8. The application according to claim 7, wherein, The polymerization reaction of the olefin monomer catalyzed by C2~C 11 includes: Add the cocatalyst and C2-C 11 olefin monomers to an organic solvent, and then inject the supported catalyst to cause the C2-C 11 olefin monomers to carry out a coordination polymerization reaction.

9. The application according to claim 8, wherein The organic solvent includes at least one of toluene, benzene, and n-heptane; The cocatalyst includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, dichloroethylaluminum, tri-n-butylaluminum, alkali metal, and alkali metal salt; The olefin monomers of C2 to C 11 include at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate, 10-undecenol, 10-undecenoic acid, 6-chloro-1-hexene, 1-hexene, and 1-octene.

10. The application according to claim 8 or 9, wherein The coordination polymerization reaction includes homopolymerization and / or copolymerization of the C2~C 11 olefin monomers.

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