Ligand compounds and methods of making, catalyst compositions and uses, catalysts and polyethylene elastomers and methods of making and uses

Abstract

The application relates to the technical field of polyolefin catalysts, and discloses a ligand compound and a preparation method thereof, a catalyst and a preparation method and application thereof, a catalyst composition and application thereof, a polyethylene elastomer and a preparation method and application thereof. The ligand compound provided by the application has large steric hindrance, and when the ligand compound is used for preparing a catalyst, the prepared catalyst has large steric hindrance, thereby having high heat resistance, can catalyze ethylene polymerization at a proper high temperature, is beneficial to industrial amplification, and can realize effective regulation of polymer molecular weight, molecular weight distribution, branching degree, content proportion of different length branches and the like by adjusting structure and polymerization conditions, so that polymers with different structures are prepared.

Description

Technical Field

[0001] This invention relates to the field of polyolefin catalyst technology, specifically to a ligand compound and its preparation method, a catalyst and its preparation method and application, a catalyst composition and its application, and a polyethylene elastomer and its preparation method and application. Background Technology

[0002] With the development of research and application of olefin resin materials, they have gradually become essential materials for people's daily lives and industrial and agricultural production, and have also become indispensable materials in cutting-edge technology, national defense construction and other fields. Among them, polyethylene materials have the characteristics of good chemical resistance, low price, simple preparation, low density and good mechanical properties.

[0003] Currently, polyethylene elastomers are mainly obtained by copolymerizing ethylene and α-olefins using metallocene catalysts. However, metallocene catalysts have drawbacks such as difficult synthesis, low yield, large amount of co-catalyst required, and high cost.

[0004] CN102180910A discloses a novel asymmetric α-diimine nickel complex catalyst, but its catalytic activity is poor and the polymerization temperature is 20℃, which is not suitable for industrial scale-up.

[0005] CN110452320A discloses a method for preparing branched polyethylene, but the specific catalyst structure is not disclosed. Furthermore, although Examples 9 and 10 yielded high catalytic activity, the prepared branched polyethylene had a high molecular weight and low degree of branching, making it unsuitable for films, modifiers, and rubber.

[0006] Therefore, there is an urgent need to develop a catalyst with high catalytic activity and polymerization conditions suitable for industrial scale-up. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of poor catalytic activity and unsuitable polymerization conditions for industrial scale-up of polyethylene elastomer catalysts in the prior art, and to provide a ligand compound and its preparation method, a catalyst and its preparation method and application, a catalyst composition and its application, and a polyethylene elastomer and its preparation method and application.

[0008] To achieve the above objectives, a first aspect of the present invention provides a ligand compound having the structure shown in formula (I):

[0009]

[0010] Among them, R 1 R 2 R 3 R 4 R 5 R6 and R 7 Each is independently selected from hydrogen, halogen, nitro, C1-C 10 Straight-chain or branched alkyl groups and C1-C 10 One of the straight-chain or branched alkoxy groups;

[0011] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0012] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl.

[0013] A second aspect of the present invention provides a method for preparing a ligand compound, comprising the following steps:

[0014] 1) In the presence of a first catalyst and a first solvent, the acenaphthoquinone shown in formula (II) is subjected to a first condensation reaction with the substituted aniline shown in formula (III) to obtain the compound shown in formula (IV);

[0015]

[0016] 2) In the presence of a second catalyst and a second solvent, the compound shown in formula (IV) is subjected to a second condensation reaction with aniline shown in formula (V) to obtain the ligand compound shown in formula (I);

[0017]

[0018] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 The definition is the same as that in the first aspect.

[0019] A third aspect of the present invention provides a ligand compound obtained by the method described in the second aspect.

[0020] A fourth aspect of the present invention provides a catalyst having the structure shown in formula (VI):

[0021]

[0022] Among them, R 1 R 2 R 3 R 4 R 5 R6 and R 7 Each is independently selected from hydrogen, halogen, nitro, C1-C 10 Straight-chain or branched alkyl groups and C1-C 10 One of the straight-chain or branched alkoxy groups;

[0023] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0024] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl at the same time;

[0025] X 1 and X 2 Each is independently selected from one of F, Cl, Br, and I.

[0026] The fifth aspect of the present invention provides a method for preparing a catalyst, wherein, under complexation reaction conditions and in the presence of an organic solvent, a ligand compound of formula (I) is subjected to a complexation reaction with a Ni-containing halide to obtain a catalyst of formula (VI).

[0027]

[0028] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 The definition is the same as that in the first aspect;

[0029]

[0030] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 X 1 and X 2 The definition is the same as that in the fourth aspect.

[0031] The sixth aspect of the present invention provides a catalyst prepared by the method described in the fifth aspect.

[0032] A seventh aspect of the present invention provides a catalyst composition comprising a main catalyst and an optional co-catalyst, wherein the main catalyst comprises the catalysts described in the fourth and sixth aspects.

[0033] The eighth aspect of the present invention provides the use of the catalysts described in the fourth and sixth aspects or the catalyst compositions described in the seventh aspect in catalytic olefin polymerization reactions.

[0034] The ninth aspect of the present invention provides a method for preparing a polyethylene elastomer, wherein ethylene is subjected to a solution polymerization reaction in the presence of the catalysts described in the fourth and sixth aspects or the catalyst composition described in the seventh aspect to obtain the polyethylene elastomer.

[0035] The tenth aspect of the present invention provides a polyethylene elastomer, which is prepared by the method described in the ninth aspect.

[0036] The eleventh aspect of this invention provides the application of the polyethylene elastomer described in the tenth aspect in the preparation of encapsulating films for solar photovoltaic cells, as a resin toughening modifier, and in the preparation of rubber.

[0037] The beneficial technical effects of the present invention through the above technical solution are as follows:

[0038] (1) The ligand compound provided by the present invention has large steric hindrance. When it is used to prepare a catalyst, the prepared catalyst can have large steric hindrance, thus having high heat resistance. It can catalyze the polymerization of ethylene at a suitable high temperature, which is beneficial for industrial scale-up. Moreover, by adjusting the structure and polymerization conditions, the molecular weight, molecular weight distribution, degree of branching, and proportion of branched chain of different lengths of polymer can be effectively controlled to obtain polymers with different structures.

[0039] (2) The catalyst provided by the present invention has the advantages of high catalytic activity, simple preparation method, low cost and stable performance. Its preparation process is simple to operate, mild reaction conditions, high yield and short preparation cycle.

[0040] (3) The present invention also provides a method for using a catalyst or a combination thereof in a polymerization reaction under mild polymerization conditions, and the resulting polyethylene elastomer material can be used in the fields of solar photovoltaic cell encapsulation film, resin toughening modifier, and rubber. Detailed Implementation

[0041] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0042] A first aspect of the present invention provides a ligand compound having the structure shown in formula (I):

[0043]

[0044] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from hydrogen, halogen, nitro, C1-C 10 Straight-chain or branched alkyl groups and C1-C 10 One of the straight-chain or branched alkoxy groups;

[0045] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0046] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl.

[0047] The ligand compound provided by this invention has large steric hindrance. When used to prepare catalysts, it can make the prepared catalysts have large steric hindrance, thus having heat resistance suitable for industrial scale-up. Moreover, by adjusting the structure and polymerization conditions, the molecular weight, molecular weight distribution, degree of branching, and proportion of branches of different lengths of polymer can be effectively controlled to obtain polymers with different structures.

[0048] In this invention, the C1-C 10 Examples of straight-chain or branched alkyl groups include, for example, any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, 2-methylhexyl, 2-ethylhexyl, 1-methylheptyl, 2-methylheptyl, n-octyl, isooctyl, n-nonyl, isononyl, and 3,5,5-trimethylhexyl.

[0049] In this invention, the C1-C 10Examples of straight-chain or branched alkoxy groups include, for example, any one of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, neopentoxy, n-hexoxy, isohexoxy, n-heptoxy, isoheptoxy, 2-methylhexoxy, 2-ethylhexoxy, 1-methylheptoxy, 2-methylheptoxy, n-octoxy, isooctoxy, n-nonoxy, isononoxy, and 3,5,5-trimethylhexoxy.

[0050] Where Ph refers to phenyl, PhF refers to phenyl with one hydrogen atom replaced by F, and the structural formula is: The substitution position of F is not fixed; for example, the substitution position can be the opposite position.

[0051] In some embodiments of the present invention, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group.

[0052] A second aspect of the present invention provides a method for preparing a ligand compound, comprising the following steps:

[0053] 1) In the presence of a first catalyst and a first solvent, the acenaphthoquinone shown in formula (II) is subjected to a first condensation reaction with the substituted aniline shown in formula (III) to obtain the compound shown in formula (IV);

[0054]

[0055] 2) In the presence of a second catalyst and a second solvent, the compound shown in formula (IV) is subjected to a second condensation reaction with aniline shown in formula (V) to obtain the ligand compound shown in formula (I);

[0056]

[0057] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 The definition is the same as that in the first aspect.

[0058] The preparation method described above in this invention has the advantages of mild conditions, simple operation, high yield, and high safety.

[0059] In some embodiments of the present invention, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group.

[0060] In some preferred embodiments of the present invention, the first catalyst in step 1) is selected from at least one of p-toluenesulfonic acid, formic acid and acetic acid.

[0061] In some preferred embodiments of the present invention, the first solvent mentioned in step 1) is selected from at least one of methanol, dichloromethane and toluene.

[0062] In some preferred embodiments of the present invention, the conditions for the first condensation reaction include: a reaction temperature of 8-40°C, for example, 8°C, 15°C, 20°C, 25°C, 32°C, 40°C, or any value within the range of any two of the above values, preferably 20-25°C; and a reaction time of 1-80 h, for example, 1 h, 5 h, 15 h, 30 h, 40 h, 55 h, 65 h, 70 h, 80 h, or any value within the range of any two of the above values, preferably 10-24 h. In the present invention, if the temperature of the first condensation reaction is too low, the reaction time will be too long or the reaction will not occur; if the temperature of the first condensation reaction is too high, side reactions will occur, and the yield will decrease; if the time of the first condensation reaction is too short, the reaction will be incomplete; if the time of the first condensation reaction is too long, side reactions are likely to occur.

[0063] In some preferred embodiments of the present invention, in step 1), the molar ratio of acenaphthene represented by formula (II) to substituted aniline represented by formula (III) is 1-3:1, for example 1:1, 1.5:1, 2:1, 2.5:1, 3:1, and any value within the range of any two of the above values, preferably 1-2:1. In the present invention, if the above molar ratio is too small, the target product cannot be obtained; if the above molar ratio is too large, raw materials are wasted.

[0064] In some preferred embodiments of the present invention, the second catalyst in step 2) is selected from at least one of p-toluenesulfonic acid, formic acid and acetic acid.

[0065] In some preferred embodiments of the present invention, the second solvent mentioned in step 2) is selected from at least one of aromatic solvents, isopropanol and n-butanol.

[0066] In some preferred embodiments of the present invention, the conditions for the second condensation reaction include: a reaction temperature of 80-150°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, and any value within the range of any two of the above values, preferably 100-120°C; and a reaction time of 1-10 hours, such as 1 hour, 2 hours, 5 hours, 7 hours, 9 hours, 10 hours, and any value within the range of any two of the above values, preferably 2-8 hours. In the present invention, if the temperature of the second condensation reaction is too low, the reaction will not occur; if the temperature of the second condensation reaction is too high, side reactions will occur, and the yield will decrease; if the time of the second condensation reaction is too short, the reaction will be incomplete; if the time of the second condensation reaction is too long, side reactions are likely to occur.

[0067] In some preferred embodiments of the present invention, in step 2), the molar ratio of the compound represented by formula (IV) to the aniline represented by formula (V) is 1:0.5-5, for example 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, and any value within the range of any two of the above values, preferably 1:1-4. In the present invention, if the above molar ratio is too small, the reaction will be incomplete; if the above molar ratio is too large, raw materials will be wasted, and side reactions are likely to occur.

[0068] In some preferred embodiments of the present invention, the method further includes: 3) purifying the ligand compound of formula (I) obtained in step 2).

[0069] In this invention, the purification method may include the following steps;

[0070] a) Remove the solvent from the solution obtained in step 2), and dissolve the resulting solid in dichloromethane;

[0071] b) Using alumina as the support, a mixed solution of petroleum ether and ethyl acetate as the eluent, column chromatography was performed using alumina, followed by thin-layer chromatography elution;

[0072] c) Remove the solvent and recrystallize using dichloromethane and methanol to obtain the purified compound shown in formula (I).

[0073] According to a particularly preferred embodiment of the present invention, a method for preparing a ligand compound includes the following steps:

[0074] 1) In the presence of a first catalyst and a first solvent, the acenaphthoquinone shown in formula (II) and the substituted aniline shown in formula (III) are subjected to a first condensation reaction at 20-25°C for 10-24 h to obtain the compound shown in formula (IV);

[0075]

[0076] 2) In the presence of a second catalyst and a second solvent, the compound shown in formula (IV) and the aniline shown in formula (V) are subjected to a second condensation reaction at 100-120°C for 2-8 h to obtain the ligand compound shown in formula (I).

[0077]

[0078] 3) Purify the ligand compound of formula (I) obtained in step 2);

[0079] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group;

[0080] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0081] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl at the same time;

[0082] The first catalyst mentioned in step 1) is selected from at least one of p-toluenesulfonic acid, formic acid, and acetic acid; the first solvent is selected from at least one of methanol, dichloromethane, and toluene.

[0083] In step 1), the molar ratio of acenaphthene as shown in formula (II) to substituted aniline as shown in formula (III) is 1-2:1;

[0084] The second catalyst mentioned in step 2) is selected from at least one of p-toluenesulfonic acid, formic acid, and acetic acid; the second solvent is selected from at least one of aromatic solvents, isopropanol, and n-butanol.

[0085] In step 2), the molar ratio of the compound represented by formula (IV) to the aniline represented by formula (V) is 1:1-4.

[0086] A third aspect of the present invention provides a ligand compound obtained by the method described in the second aspect.

[0087] A fourth aspect of the present invention provides a catalyst having the structure shown in formula (VI):

[0088]

[0089] Among them, R1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently selected from hydrogen, halogen, nitro, C1-C 10 Straight-chain or branched alkyl groups and C1-C 10 One of the straight-chain or branched alkoxy groups;

[0090] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0091] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl at the same time;

[0092] X 1 and X 2 Each is independently selected from one of F, Cl, Br, and I.

[0093] The catalyst provided by this invention has large steric hindrance, thus exhibiting high heat resistance suitable for industrial scale-up. Furthermore, by adjusting the structure and polymerization conditions, it is possible to effectively control the polymer's molecular weight, molecular weight distribution, degree of branching, and the proportion of branches of different lengths, thereby obtaining polymers with different structures. The catalyst of this invention has advantages such as high catalytic activity, simple preparation method, low cost, and stable performance.

[0094] In some embodiments of the present invention, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group.

[0095] In some preferred embodiments of the present invention, X 1 and X 2 Each can be either Cl or Br.

[0096] In some embodiments of the present invention, the catalyst is selected from at least one of the following complexes:

[0097] Complex Ni1: where R 4 =R 5 =Me,X 1 =X 2 =Br, other substituents are H;

[0098] Complex Ni2: where R 1 =R 4 =R 5 =Me,X 1 =X 2 =Br, other substituents are H;

[0099] Complex Ni3: where R 1 =R 3 =R 5 =Et,X 1 =X 2 =Br, other substituents are H;

[0100] Complex Ni4: where R 1 =Et,R 5 =Me,X 1 =X 2 =Br, other substituents are H;

[0101] Complex Ni5: where R 1 =iPr,R 5 =Me,X 1 =X 2 =Br, other substituents are H.

[0102] Where Me is methyl, Et is ethyl, iPr is isopropyl, and other substituents refer to R groups without specific descriptions, such as R in the complex Ni1. 1 R 2 R 3 R 6 R 7 .

[0103] The fifth aspect of the present invention provides a method for preparing a catalyst, wherein, under complexation reaction conditions and in the presence of an organic solvent, a ligand compound of formula (I) is subjected to a complexation reaction with a Ni-containing halide to obtain a catalyst of formula (VI).

[0104]

[0105] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 The definition is the same as that in the first aspect;

[0106]

[0107] Among them, R 1 R2 R 3 R 4 R 5 R 6 R 7 X 1 and X 2 The definition is the same as that in the fourth aspect.

[0108] The preparation method described above in this invention has the advantages of mild conditions, simple operation, high yield, and high safety.

[0109] In some embodiments of the present invention, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group.

[0110] In some preferred embodiments of the present invention, X 1 and X 2 Each can be either Cl or Br.

[0111] In some preferred embodiments of the present invention, the conditions for the complexation reaction include: being carried out in the presence of a protective gas; a reaction temperature of 8-40°C, for example 8°C, 12°C, 18°C, 23°C, 30°C, 36°C, 40°C, and any value within the range of any two of the above values, preferably 10-35°C; and a reaction time of 3-12h, for example 3h, 5h, 8h, 9h, 11h, 12h, and any value within the range of any two of the above values, preferably 4-10h.

[0112] In this invention, the protective gas is preferably N2.

[0113] In some preferred embodiments of the present invention, the organic solvent is selected from at least one of alcohol solvents, dichloromethane, and chloroform.

[0114] In some preferred embodiments of the present invention, the Ni-containing halide is (DME)NiBr2 or NiCl2·6H2O.

[0115] In some preferred embodiments of the present invention, the molar ratio of the ligand compound represented by formula (I) to the Ni-containing halide is 0.5-3:1, for example 0.5:1, 1:1, 2:1, 3:1, and any value within the range of any two of the above values, preferably 1-2:1. In the present invention, a molar ratio that is too large or too small will result in waste of raw materials.

[0116] According to a particularly preferred embodiment of the present invention, a method for preparing a catalyst is provided, wherein a ligand compound of formula (I) is subjected to a complexation reaction with a Ni-containing halide at 10-35°C for 4-10 h in the presence of a protective gas and an organic solvent to obtain a catalyst of formula (VI).

[0117]

[0118] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group;

[0119] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0120] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl at the same time;

[0121]

[0122] Among them, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each is independently hydrogen or a C1-C6 straight-chain or branched alkyl group;

[0123] Where R 3 When it is hydrogen, R 1 and R 5 It may not be methyl, ethyl, or isopropyl at the same time;

[0124] When R 3 When it is methyl, R 1 and R 5 It can be either methyl or ethyl at the same time;

[0125] X 1 and X 2 Each can be either Cl or Br;

[0126] The organic solvent is selected from at least one of alcohol solvents, dichloromethane, and chloroform;

[0127] The Ni-containing halide is (DME)NiBr2 or NiCl2·6H2O;

[0128] The molar ratio of the ligand compound represented by formula (I) to the Ni-containing halide is 1-2:1.

[0129] The sixth aspect of the present invention provides a catalyst prepared by the method described in the fifth aspect.

[0130] A seventh aspect of the present invention provides a catalyst composition comprising a main catalyst and an optional co-catalyst, wherein the main catalyst comprises the catalysts described in the fourth and sixth aspects.

[0131] In some preferred embodiments of the present invention, the molar ratio of the co-catalyst to the main catalyst is 100-4000:1, based on the metal elements contained therein.

[0132] In some preferred embodiments of the present invention, the co-catalyst is selected from at least one of aluminoxane, alkylaluminum, and alkylaluminum chloride.

[0133] In some preferred embodiments of the present invention, the aluminum oxane is methylaluminoxane or triisobutylaluminum-modified methylaluminoxane.

[0134] In some preferred embodiments of the present invention, the alkylaluminum chloride is selected from at least one of trimethylaluminum chloride, diethylaluminum chloride, trichlorotriethylaluminum, triisobutylaluminum chloride, triethylaluminum chloride, monochlorodiethylaluminum chloride, and diethylzinc chloride.

[0135] The eighth aspect of the present invention provides the use of the catalysts described in the fourth and sixth aspects or the catalyst compositions described in the seventh aspect in catalytic olefin polymerization reactions.

[0136] In some preferred embodiments of the present invention, the olefin polymerization reaction is an ethylene polymerization reaction.

[0137] The ninth aspect of the present invention provides a method for preparing a polyethylene elastomer, wherein ethylene is subjected to a solution polymerization reaction in the presence of the catalysts described in the fourth and sixth aspects or the catalyst composition described in the seventh aspect to obtain the polyethylene elastomer.

[0138] In some preferred embodiments of the present invention, the conditions for the solution polymerization reaction include: a polymerization temperature of 0-100°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any value within any range of any two of the above values; a polymerization pressure of 0.1-3 MPa, for example, 0.1 MPa, 0.5 MPa, 1 MPa, 1.2 MPa, 1.8 MPa, 2.2 MPa, 2.5 MPa, 3 MPa, or any value within any range of any two of the above values; and a polymerization time of 10-60 min. In this invention, if the solution polymerization temperature is too low, the polymer has a high molecular weight, low melt index, low branching degree, and high melting point; if the solution polymerization temperature is too high, the polymer has a low molecular weight, high melt index, high branching degree, and low or no melting point; if the solution polymerization pressure is too low, the polymer has a low molecular weight, high melt index, high branching degree, and low or no melting point; if the solution polymerization pressure is too high, the polymer has a high molecular weight, low melt index, low branching degree, and high melting point; if the solution polymerization time is too short, the catalytic activity cannot be fully utilized; if the solution polymerization time is too long, the catalytic activity is low in the later stages, the reaction is slow, and the economy is poor.

[0139] The tenth aspect of the present invention provides a polyethylene elastomer, which is prepared by the method described in the ninth aspect.

[0140] In some preferred embodiments of the present invention, the polyethylene elastomer comprises a polyethylene main chain and a plurality of C1 or higher alkyl side chains bonded to the polyethylene main chain; the total number of methyl side chains corresponding to every 1000 carbon atoms in the polyethylene main chain is 30-120, for example 30, 40, 50, 60, 70, 80, 90, 100, 110, 120; the total number of ethyl, propyl, butyl, and pentyl side chains is 5-60, for example 5, 10, 20, 30, 40, 50, 60; and the total number of C6 or higher alkyl side chains is 2-50, for example 2, 5, 10, 20, 30, 40, 50.

[0141] Alkyl side chains with 6 or more carbon atoms refer to alkyl side chains that have been detected to have 6 or more carbon atoms.

[0142] In some preferred embodiments of the present invention, the melt flow rate of the polyethylene elastomer at 190°C and a load of 2.16 kg is 0.01-25 g / 10 min, for example 0.01 g / 10 min, 0.1 g / 10 min, 1 g / 10 min, 3 g / 10 min, 5 g / 10 min, 10 g / 10 min, 12 g / 10 min, 18 g / 10 min, 20 g / 10 min, 22 g / 10 min, 25 g / 10 min, and any value within any range of any two of the above values, preferably 0.1-20 g / 10 min, and more preferably 4-20 g / 10 min.

[0143] In this invention, the number of side chains in the molecular chain of polyethylene elastomer is determined by 1H NMR spectroscopy, and the melt flow rate (melt index) is determined according to standard ASTM D1238 under conditions of 190°C and 2.16 kg.

[0144] The eleventh aspect of this invention provides the application of the polyethylene elastomer described in the tenth aspect in the preparation of encapsulating films for solar photovoltaic cells, as a resin toughening modifier, and in the preparation of rubber.

[0145] Using the polyethylene elastomer described in this invention to prepare encapsulating films for solar photovoltaic cells, as a resin toughening modifier, and in the preparation of rubber can achieve effects such as improved product performance, increased production efficiency, and reduced energy consumption.

[0146] The present invention will be described in detail below through embodiments.

[0147] Unless otherwise specified in the following examples and comparative examples, all conditions were performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available products.

[0148] Test method:

[0149] (1) Melting point:

[0150] DSC testing was used, with a temperature range of 0-120℃. The temperature change process was as follows:

[0151] First stage: From room temperature to 120℃, heating rate is 10℃ / min, and then hold at 120℃ for 2min;

[0152] Second stage: Cool down from 120℃ to 0℃ at a rate of 10℃ / min, and hold at 0℃ for 2 minutes;

[0153] The third stage: from 0℃ to 120℃, the heating rate is 10℃ / min, and then the temperature drops to 40℃, at which point the test ends.

[0154] The melting point is determined from the melting peak of the third heating curve.

[0155] (2) Melt flow rate (melt index): Tested according to standard ASTM D1238 at 190°C and 2.16 kg.

[0156] (3) Film transparency: measured according to GBT 2410-2008 standard.

[0157] (4) Catalytic activity ratio: The ratio of the weight of the polymer produced to the weight of the catalyst used.

[0158] Preparation Example 1

[0159] This preparation example illustrates the preparation of ligand compound L1.

[0160] (1) In a 250 mL round-bottom flask, 3.23 g (10 mmol) of 2-bis(p-fluorophenyl)methyl-4,6-dimethylaniline, 2.19 g (12 mmol) of acenaphthoquinone, 1.08 g (catalyst amount) of p-toluenesulfonic acid, 150 mL of methanol, and 6 mL of dichloromethane were added. After stirring at room temperature for 24 h, the mixture was filtered and dried to obtain a yellow solid. Its structural formula is shown below, and its yield was 45%.

[0161]

[0162] The structural evidence is as follows:

[0163] 1 H NMR (400MHz, CDCl3, TMS): δ8.29(1H),8.13(1H),7.86(1H),7.70(1H),7.14(1H),7.04– 6.92(5H),6.77(2H),6.62(1H),6.32(1H),6.01(2H),5.64(s,1H),2.33(3H),2.24(3H).

[0164] (2) In a 100 mL round-bottom flask, 2-(2-di(p-fluorophenyl)methyl-4,6-dimethylaniline)acenaphthene (C1, 0.49 g, 1 mmol), 2,3-dimethylaniline (0.18 g, 1.5 mmol), a catalyst amount of p-toluenesulfonic acid (0.13 g), and toluene (30 mL) were added. The mixture was heated to reflux and reacted for 4 h. The solvent was removed using a rotary evaporator. The remaining solid was supported on alumina and column chromatography was performed using a mixed solution of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate was 50:1) as the eluent. The eluent fraction was detected by thin-layer chromatography (using a mixed solution of petroleum ether and ethyl acetate (volume ratio of 3:1), and the second fraction was collected). After removing the solvent, the solid was recrystallized from dichloromethane and methanol, filtered, and dried to obtain a yellow solid. The structural formula of ligand compound L1 is shown below, with a yield of 35%.

[0165]

[0166] The structural evidence is as follows:

[0167] 1 H NMR (400MHz, CDCl3, TMS): δ7.85–7.77(2H),7.31(1H),7.20(2H),7.10–6.88(9H),6.64(1 H),6.56(1H),6.41(1H),6.16(2H),5.69(1H),2.33(3H),2.27(3H),2.14(3H),2.03(3H).

[0168] 13 C NMR(100MHz, CDCl3, TMS):162.5,162.3,162.1,161.6,160.3,159.3,149.5, 146.4,140.3,139.1,137.6,133.1,132.7,131.5,131.3,131.0,130.5,129. 8,129.2,129.0,128.8,128.5,128.4,128.3,127.7,127.6,125.3,124.9,123.9,122.9,122.4,115.1,114.9,114.2,114.3,51.1,21.4,20.4,17.6,17.4.

[0169] Elemental analysis: C 41 H 32 F2N2 (590.72): C, 83.36; H, 5.46; N, 4.74%. Found: C, 83.15; H, 5.56; N, 4.72%.

[0170] Preparation Example 2

[0171] This preparation example illustrates the preparation of the ligand compound L2.

[0172] The preparation was carried out according to the method of Preparation Example 1, except that the aniline compound involved in the reaction was 2,3,6-trimethylaniline. The structural formula of ligand compound L2 is shown below, and its yield was 37%.

[0173]

[0174] The structural evidence is as follows:

[0175] 1 H NMR (400MHz, CDCl3, TMS): δ7.85–7.77(2H),7.31(1H),7.20(2H),7.10–6.88(9H),6.64(1H),6 .56(1H),6.41(1H),6.16(2H),5.69(1H),2.33(3H),2.27(3H),2.14(3H),2.08(3H),2.03(3H).

[0176] 13 C NMR (100MHz, CDCl3, TMS): δ162.4,162.8,162.1,161.4,160.3,159.6,149.3, 146.4,140.3,139.1,137.6,133.1,132.7,131.4,131.5,131.0,130.6,129.4, 129.2,129.1,128.7,128.5,128.4,128.1,127.8,127.6,125.1,125.0,123.9,122.9,122.3,115.0,114.9,114.5,114.3,51.1,21.6,20.5,18.4,17.6,17.1.

[0177] Elemental analysis: C 42 H 34 F2N2 (604.74): C, 83.42; H, 5.67; N, 4.63%. Found: C, 83.53; H, 5.41; N, 4.52%.

[0178] Preparation Example 3

[0179] This preparation example illustrates the preparation of the ligand compound L3.

[0180] The preparation was carried out according to the method of Preparation Example 1, except that the aniline compound involved in the reaction was 2,4,6-diethylaniline. The structural formula of ligand compound L3 is shown below, and its yield was 32%.

[0181]

[0182] The structural evidence is as follows:

[0183] 1 H NMR (400MHz, CDCl3, TMS): δ7.83–7.78(2H),7.31(1H),7.15(1H),7.06–6.89(9H),6.64(2H),6.38(1H),6. 17(2H),5.69(1H),2.78–2.69(2H),2.60–2.51(4H),2.43(3H),2.32(3H),2.06(3H),1.42(3H),1.12(6H).

[0184] 13 C NMR (100MHz, CDCl3, TMS): δ162.8,162.6,161.6,161.5,160.0,159.2,146.5, 145.8,140.1,139.1,137.7,133.2,132.9,132.6,131.4,131.2,130.9,130.5, 129.6,129.0,128.8,128.7,127.8,127.7,127.4,127.2,127.1,125.5,122.8,122.7,115.0,114.8,114.5,114.4,51.0,24.8,24.1,21.2,17.5,14.8,13.9.

[0185] Elemental analysis: C 45 H 40 F2N2 (646.83): C, 83.56; H, 6.23; N, 4.33%. Found: C, 83.21; H, 6.37; N, 4.20%.

[0186] Preparation Example 4

[0187] This preparation example illustrates the preparation of the ligand compound L4.

[0188] The preparation was carried out according to the method of Preparation Example 1, except that the aniline compound involved in the reaction was 2-methyl-6-ethylaniline. The structural formula of ligand compound L4 is shown below, and its yield was 40%.

[0189]

[0190] The structural evidence is as follows:

[0191] 1 H NMR (400MHz, CDCl3, TMS): δ7.83–7.77(2H),7.31(1H),7.23–7.01(11H),6.65(1H),6.60(1H) ,6.40(1H),6.18(2H),5.72(1H),2.74–2.65(2H),2.33(3H),2.24(3H),2.10(3H),1.18(3H).

[0192] 13 C NMR (100MHz, CDCl3, TMS): δ162.2,162.5,161.6,161.3,160.2,159.2,148.4,146.4 ,140.2,139.1,137.8,137.7,133.0,132.7,131.3,131.2,130.9,130.7,130.6,130 .4,129.7,129.0,128.9,128.7,127.8,127.6,127.4,126.5,126.4,126.0,125.0,124.1,122.8,122.6,115.0,114.8,114.4,114.2,50.9,24.7,21.3,18.5,17.5,13.5.

[0193] Elemental analysis: C 42 H 34 F2N2 (604.27): C, 83.42; H, 5.67; N, 4.63%. Found: C, 83.32; H, 5.73; N, 4.42%.

[0194] Preparation Example 5

[0195] This preparation example illustrates the preparation of ligand compound L5.

[0196] The preparation was carried out according to the method of Preparation Example 1, except that the aniline compound involved in the reaction was 2-methyl-6-isopropylaniline. The structural formula of ligand compound L5 is shown below, and its yield was 32%.

[0197]

[0198] The structural evidence is as follows:

[0199] 1H NMR (400MHz, CDCl3, TMS): δ7.82–7.76(2H),7.31–7.25(3H),7.16(1H),7.08–7.03(4H),7.00–6.88(4H),6.65(1H) ,6.57(1H),6.38(1H),6.17(2H),5.71(1H),3.05–2.98(1H),2.34(3H),2.23(3H),2.08(3H),1.20(3H),1.08(3H).

[0200] 13 C NMR (100MHz, CDCl3, TMS): δ162.6,162.5,161.6,160.1,159.1,147.1,146.4 ,140.2,139.1,137.7,135.5,135.4,133.0,132.6,131.3,131.2,130.9,130 .4,129.7,128.9,128.8,128.7,127.6,127.4,125.0,124.5,123.7,123.4,123.0,122.8,115.0,114.8,114.4,114.2,50.9,28.6,23.4,21.3,18.2,17.5.

[0201] Elemental analysis: C 43 H 36 F2N2 (618.77): C, 83.47; H, 5.86; N, 4.53%. Found: C, 83.54; H, 5.62; N, 4.73%.

[0202] Example 1

[0203] This example illustrates the preparation of the catalyst-complex Ni1.

[0204] In a 25 mL Shrek flask, ligand compound L1 (0.12 g, 0.21 mmol) obtained in Preparation Example 1, (DME)NiBr2 (0.06 g, 0.2 mmol), and dichloromethane (10 mL) were added. The solution was stirred at room temperature under N2 atmosphere for 24 h. The solvent was removed under reduced pressure, and a solid precipitated upon the addition of diethyl ether. The solid was filtered, washed with diethyl ether, and dried to obtain a red solid. The structural formula of the complex Ni1 is shown below, with a yield of 87%.

[0205]

[0206] The structural evidence is as follows:

[0207] Elemental analysis: C 41 H32 F2N2NiBr2 (809.22): C, 60.86; H, 3.99; N, 3.46%. Found: C, 61.04; H, 4.01; N, 3.32%.

[0208] Example 2

[0209] This example illustrates the preparation of the catalyst-complex Ni2.

[0210] Prepared according to the method of Example 1, except that the ligand compound involved in the reaction is L2 as described in Preparation Example 2. The structural formula of the complex Ni2 is shown below, with a yield of 94%.

[0211]

[0212] The structural evidence is as follows:

[0213] Elemental analysis: C 42 H 34 F2N2NiBr2 (823.25): C, 61.28; H, 4.16; N, 3.40%. Found: C, 61.32; H, 4.07; N, 3.32%.

[0214] Example 3

[0215] This example illustrates the preparation of the catalyst-complex Ni3.

[0216] Prepared according to the method of Example 1, except that the ligand compound involved in the reaction is L3 as described in Preparation Example 3. The structural formula of the complex Ni3 is shown below, with a yield of 88%.

[0217]

[0218] The structural evidence is as follows:

[0219] Elemental analysis: C 45 H 40 F2N2NiBr2 (865.33): C, 62.46; H, 4.66; N, 3.24%. Found: C, 62.65; H, 4.57; N, 3.48%.

[0220] Example 4

[0221] This example illustrates the preparation of the catalyst-complex Ni4.

[0222] Prepared according to the method of Example 1, except that the ligand compound involved in the reaction is L4 as described in Preparation Example 4. The structural formula of the complex Ni4 is shown below, with a yield of 92%.

[0223]

[0224] The structural evidence is as follows:

[0225] Elemental analysis: C 42 H 34 F2N2NiBr2 (823.25): C, 61.28; H, 4.62; N, 3.40%. Found: C, 61.56; H, 4.58; N, 3.51%.

[0226] Example 5

[0227] This example illustrates the preparation of the catalyst-complex Ni5.

[0228] Prepared according to the method of Example 1, except that the ligand compound involved in the reaction is L5 as described in Preparation Example 5. The structural formula of the complex Ni5 is shown below, with a yield of 93%.

[0229]

[0230] The structural evidence is as follows:

[0231] Elemental analysis: C 43 H 36 F2N2NiBr2 (837.27): C, 61.69; H, 4.33; N, 3.35%. Found: C, 61.62; H, 4.46; N, 3.27%.

[0232] Application Example 1

[0233] This application example illustrates the preparation of polyethylene elastomer P1.

[0234] After anhydrous and oxygen-free treatment of a 5L polymerization reactor, a vacuum was drawn, and 3L of hexane was added, followed by a hexane solution of 0.02g of the main catalyst (Ni1) and 4.0mL of 1M trichlorotriethylaluminum. Ethylene was continuously introduced, and the reaction temperature was controlled at 60℃. The gas inlet rate was controlled to maintain the pressure inside the reactor at 0.8MPa, and the reaction time was 30min. After the reaction was completed, the gel was discharged, washed with an ethanol-water solution, and finally devolatilized, extruded, and granulated to obtain polyethylene elastomer P1.

[0235] Tests showed that the catalyst used had a catalytic activity ratio of 13000gPE / g catalyst, the polyethylene elastomer P1 had a melting point of 74℃, a branching degree of 75 branches / 1000℃ (including 62 C1 side chains, 10 C2-C5 side chains, and 3 long side chains above C6), a melt index of 6g / 10min (190℃, 2.16kg), and a film transparency of ≥90%, which is comparable to the photovoltaic-grade POE specifications on the market, and can be used to prepare photovoltaic encapsulant films.

[0236] Application Example 2

[0237] This application example illustrates the preparation of polyethylene elastomer P2.

[0238] After anhydrous and oxygen-free treatment of a 5L polymerization reactor, a vacuum was drawn, and 3L of hexane was added, followed by a hexane solution of 0.02g of the main catalyst (Ni2) and 4.0mL of 1M trichlorotriethylaluminum. Ethylene was continuously introduced, and the reaction temperature was controlled at 75℃. The gas inlet rate was controlled to maintain the pressure inside the reactor at 1.0MPa, and the reaction time was 30min. After the reaction was completed, the gel was discharged, washed with an ethanol-water solution, and finally devolatilized, extruded, and granulated to obtain polyethylene elastomer P2.

[0239] Tests showed that the catalyst used had a catalytic activity ratio of 10500gPE / g catalyst, the polyethylene elastomer P2 had a melting point of 60℃, a branching degree of 110 branches / 1000℃ (including 77 C1 side chains, 24 C2-C5 side chains, and 9 long side chains above C6), a melt index of 15g / 10min (190℃, 2.16kg), and a film transparency of ≥90%, which is comparable to the photovoltaic-grade POE index on the market, and can be used to prepare photovoltaic encapsulant films.

[0240] Application Example 3

[0241] This application example illustrates the preparation of polyethylene elastomer P3.

[0242] After anhydrous and oxygen-free treatment of a 5L polymerization reactor, a vacuum was drawn, and 3L of hexane was added, followed by a hexane solution of 0.02g of the main catalyst (Ni3) and 4.0mL of 2M diethylaluminum chloride. Ethylene was continuously introduced, and the reaction temperature was controlled at 80℃. The gas inlet rate was controlled to maintain the pressure inside the reactor at 1.2MPa, and the reaction time was 30min. After the reaction was completed, the gel was discharged, washed with an ethanol-water solution, and finally devolatilized, extruded, and granulated to obtain polyethylene elastomer P3.

[0243] Tests showed that the catalyst used had a catalytic activity ratio of 9000gPE / g catalyst, a melting point of 59℃ for polyethylene elastomer P3, a branching degree of 108 branches / 1000℃ (including 76 C1 side chains, 23 C2-C5 side chains, and 9 long side chains above C6), and a melt index of 0.4g / 10min (190℃, 2.16kg). These results are comparable to the POE indicators used in toughening modifiers on the market, making it suitable for use as a resin toughening modifier.

[0244] Application Example 4

[0245] This application example illustrates the preparation of polyethylene elastomer P4.

[0246] After anhydrous and oxygen-free treatment of a 5L polymerization reactor, a vacuum was drawn, and 3L of hexane was added, followed by a hexane solution of 0.02g of the main catalyst (Ni4) and 4.0mL of 2M diethylaluminum chloride. Ethylene was continuously introduced, and the reaction temperature was controlled at 85℃. The gas inlet rate was controlled to maintain the pressure inside the reactor at 2MPa, and the reaction time was 30min. After the reaction was completed, the gel was discharged, washed with an ethanol-water solution, and finally devolatilized, extruded, and granulated to obtain polyethylene elastomer P4.

[0247] The catalyst used was tested and found to have a catalytic activity ratio of 8000gPE / g catalyst. The melting point of the polyethylene elastomer P4 was 30℃, and the degree of branching was 150 branches / 1000℃ (including 102 C1 side chains, 33 C2-C5 side chains, and 15 long side chains above C6). The melt index was 0.2g / 10min (190℃, 2.16kg). It can be used as a toughening modifier for low-melting-point resins.

[0248] Application Example 5

[0249] This application example illustrates the preparation of polyethylene elastomer P5.

[0250] After anhydrous and oxygen-free treatment of a 5L polymerization reactor, a vacuum was drawn, and 3L of hexane was added, followed by a hexane solution containing 0.02g of the main catalyst (Ni5) and 16mL of 1M methylaluminoxane. Ethylene was continuously introduced, and the reaction temperature was controlled at 90℃. The gas inlet rate was controlled to maintain the pressure inside the reactor at 2.5MPa, and the reaction time was 30min. After the reaction was completed, the gel was discharged, washed with an ethanol-water solution, and finally devolatilized, extruded, and granulated to obtain polyethylene elastomer P5.

[0251] The catalyst used was tested and found to have a catalytic activity ratio of 8000gPE / g catalyst. The test results showed that polyethylene elastomer P5 is a completely amorphous material with no melting point and a branching degree of 175 branches / 1000°C (including 117 C1 side chains, 38 C2-C5 side chains, and 20 long side chains above C6). The melt index is 0.1g / 10min (190°C, 2.16kg), and it can be used to prepare rubber.

[0252] Comparative Example 1

[0253] The preparation method is the same as in Application Example 1, except that the main catalyst is C2 in CN102180910A, and polyethylene elastomer CP2 is obtained.

[0254] The catalyst used was tested and found to have a catalytic activity ratio of 2000gPE / g catalyst, which is relatively low. The polyethylene elastomer CP2 has no melting point and a branching degree of 190 branches / 1000°C (126 C1 side chains, 42 C2-C5 side chains, and 22 long side chains above C6). The melt index is 10g / 10min (190°C, 2.16kg).

[0255] Comparative Example 2

[0256] The preparation method is the same as in Application Example 1, except that the main catalyst is C4 in CN102180910A, and polyethylene elastomer CP3 is obtained.

[0257] Tests showed that the catalyst used had a catalytic activity ratio of 4500gPE / g catalyst, which was relatively low. The melting point of polyethylene elastomer CP3 was 80℃, and the degree of branching was 66 branches / 1000℃ (55 C1 side chains, 10 C2-C5 side chains, and 1 long side chain above C6). The melt index was too low to be measured (190℃, 2.16kg).

[0258] The test results show that the catalysts used in Application Examples 1-5 of this invention have higher catalytic activity. Under their catalytic action, the melting point and melt index of the polyethylene elastomer obtained by catalyzing the ethylene polymerization reaction can be controlled and combined over a wide range. Furthermore, the melting point and melt index can be reasonably matched to meet the actual needs of different applications, thereby preparing polyolefin elastomers with a wide range of properties.

[0259] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A ligand compound characterized in that, The ligand compound has a structure shown in formula (I): Formula (I) The structure shown in formula (I) is selected from at least one of L1-L5: 。 2. A method of preparing a ligand compound, characterized by, The method comprises the following steps: 1) a first condensation reaction of acenaphthenequinone shown in formula (II) with substituted aniline shown in formula (III) in the presence of a first catalyst and a first solvent, to obtain a compound shown in formula (IV); Formula (II) Formula (III) Formula (IV) 2) a second condensation reaction of the compound shown in formula (IV) with aniline shown in formula (V) in the presence of a second catalyst and a second solvent, to obtain the ligand compound shown in formula (I); Formula (V) Formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same as defined in claim 1.

3. The method of claim 2, wherein, The first catalyst in step 1) is selected from at least one of p-toluenesulfonic acid, formic acid and acetic acid; And / or, the first solvent in step 1) is selected from at least one of methanol, dichloromethane and toluene; And / or, the conditions of the first condensation reaction include: the reaction temperature is 8-40℃; the reaction time is 1-80h; And / or, in step 1), the molar feeding ratio of acenaphthenequinone shown in formula (II) to substituted aniline shown in formula (III) is 1-3:1; The second catalyst in step 2) is selected from at least one of p-toluenesulfonic acid, formic acid and acetic acid; And / or, the second solvent in step 2) is selected from at least one of aromatic hydrocarbon solvents, isopropanol and n-butanol; And / or, the conditions of the second condensation reaction include: the reaction temperature is 80-150℃; the reaction time is 1-10h; And / or, in step 2), the molar feeding ratio of the compound shown in formula (IV) to aniline shown in formula (V) is 1:0.5-5; And / or, the method further comprises: 3) purifying the ligand compound shown in formula (I) obtained in step 2).

4. The method of claim 3, wherein, The conditions of the first condensation reaction include: the reaction temperature is 20-25℃; the reaction time is 10-24h; And / or, in step 1), the molar feeding ratio of acenaphthenequinone shown in formula (II) to substituted aniline shown in formula (III) is 1-2:1; And / or, the conditions of the second condensation reaction include: the reaction temperature is 100-120℃; the reaction time is 2-8h; And / or, in step 2), the molar feeding ratio of the compound shown in formula (IV) to aniline shown in formula (V) is 1:1-4.

5. A catalyst characterized by, The catalyst has a structure shown in formula (VI): Formula (VI) The catalyst is selected from at least one of the following complexes: Complex Ni1: where R 4 = R 5 = Me, X 1 = X 2 = Br, and other substituents are H; Complex Ni2: where R 1 = R 4 =R 5 = Me, X 1 = X 2 = Br, other substituents are H; Complex Ni3: where R 1 = R 3 = R 5 = Et, X 1 = X 2 = Br, and the other substituents are H; Complex Ni4: where R 1 = Et, R 5 = Me, X 1 = X 2 = Br, and the other substituents are H; Complex Ni5: where R 1 = i Pr, R 5 = Me, X 1 = X 2 = Br, other substituents are H.

6. A method for producing a catalyst, characterized by, The ligand compound shown in formula (I) is subjected to a complexation reaction with a Ni-containing halide in the presence of complexation reaction conditions and an organic solvent, to obtain the catalyst shown in formula (VI); Formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same as defined in claim 1 ; Formula (VI) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 and X 2 are defined as in claim 5.

7. The method of claim 6, wherein, The conditions of the complexation reaction include: being carried out in the presence of a protective gas; the reaction temperature is 8-40℃; the reaction time is 3-12h; And / or, the organic solvent is selected from at least one of alcohol solvents, dichloromethane and chloroform; And / or, the Ni-containing halide is (DME)NiBr2; And / or, the molar ratio of the ligand compound shown in formula (I) to the Ni-containing halide is 0.5-3:

1.

8. The method of claim 7, wherein, The conditions of the complexation reaction include: being carried out in the presence of a protective gas; the reaction temperature is 10-35℃; the reaction time is 4-10h; And / or, the molar ratio of the ligand compound shown in formula (I) to the Ni-containing halide is 1-2:

1.

9. A catalyst prepared by the method of any one of claims 6-8.

10. A catalyst composition characterized in that, The composition comprises a main catalyst and an optional cocatalyst, the main catalyst comprising the catalyst of any one of claims 5 and 9.

11. The catalyst composition of claim 10, wherein, The molar ratio of the cocatalyst to the main catalyst, in terms of the contained metal elements, is 100-4000:1; And / or, the cocatalyst is selected from at least one of aluminoxane, aluminum alkyl and aluminum alkyl chloride.

12. The catalyst composition of claim 11, wherein, The aluminoxane is methyl aluminoxane or methyl aluminoxane modified by triisobutyl aluminum; And / or, the aluminum alkyl chloride is selected from at least one of diethyl aluminum chloride and triethyl aluminum chloride.

13. Use of the catalyst of any one of claims 5 and 9 or the catalyst composition of any one of claims 10-12 in catalyzing an olefin polymerization reaction.

14. Use according to claim 13, wherein, The olefin polymerization reaction is an ethylene polymerization reaction.

15. A process for the preparation of a polyethylene elastomer, characterized in that, Ethylene is subjected to a solution polymerization reaction in the presence of the catalyst of any one of claims 5 and 9 or the catalyst composition of any one of claims 10-12 to obtain a polyethylene elastomer.

16. The method of making a polyethylene elastomer according to Claim 15, wherein, The conditions of the solution polymerization reaction include: a polymerization temperature of 0-100℃, a polymerization pressure of 0.1-3MPa, and a polymerization time of 10-60min.

17. A polyethylene elastomer prepared by the method of claim 15 or 16.

18. The polyethylene elastomer of claim 17, wherein, The polyethylene elastomer comprises a polyethylene main chain and a plurality of alkyl side chains with carbon number of 1 or more bonded to the polyethylene main chain; the total number of methyl side chains corresponding to 1000 carbon atoms in the polyethylene main chain is 30-120, the total number of ethyl, propyl, butyl and pentyl side chains is 5-60, and the total number of alkyl side chains with carbon number of 6 or more is 2-50; And / or, the melt flow rate of the polyethylene elastomer under a load of 2.16kg at 190℃ is 0.01-25g / 10min.

19. The polyethylene elastomer of claim 18, wherein, The melt flow rate of the polyethylene elastomer under a load of 2.16kg at 190℃ is 0.1-20g / 10min.

20. Use of the polyethylene elastomer of any one of claims 17-19 in preparing a solar photovoltaic cell encapsulation adhesive film, as a resin toughening modifier, and in preparing rubber.

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