Organic polymer carrier, ethylene oligomerization catalyst system, and preparation method therefor and use thereof

Abstract

Provided in the present invention are an organic polymer carrier, an ethylene oligomerization catalyst system, and a preparation method therefor and the use thereof The organic polymer carrier is obtained by copolymerizing a monomer comprising divinyl benzene and a monomer containing a bidentate pyridine-imine ligand, wherein the monomer containing the bidentate pyridine-imine ligand has a structure as represented by formula I: formula I. In formula I, R1 and R2 are each independently selected from H, halogen, and C1-C7 alkyl and derivatives thereof; R3 is selected from H, halogen, C1-C7 alkyl and derivatives thereof, and C6-C10 aryl and derivatives thereof; R4 is selected from H, and C1-C4 alkyl and derivatives thereof; and x is 0-3. The catalyst system has good ethylene oligomerization activity and α-olefin selectivity and long service life.

Description

An organic polymer carrier, ethylene oligomerization catalyst system and its preparation method and application Technical Field

[0001] The present invention belongs to the field of ethylene oligomerization catalysts, and in particular relates to an organic polymer carrier, an ethylene oligomerization catalyst system, and a preparation method and application thereof. Background Art

[0002] Ethylene oligomerization is the most important method for producing high-purity even-carbon α-olefins. Alpha-olefins with 4-20 carbon atoms are key raw materials for the production of surfactants, plasticizers, synthetic lubricants, linear polyolefins, and polyolefin elastomers. Patents US3444263, US3510539, and US3789081 used the Ziegler-Natta process with triethylaluminum as a catalyst to produce linear α-olefins. However, the large amount of alkyl aluminum used in the reaction made the reaction difficult to control. Later, patent US3644563 used a phosphine oxide bidentate nickel complex as a catalyst, the famous SHOP catalyst system, which successfully achieved industrialization of ethylene oligomerization and was a major breakthrough in the field of ethylene oligomerization. The SHOP process offers high activity and high product quality, but multiple isomerization and disproportionation processes result in a lengthy process flow and high investment. Patents EP241596 and EP320571 use a catalyst system composed of zirconium tetrachloride and alkylaluminum to carry out ethylene oligomerization through a one-step process. The process reaction conditions are mild, and the alpha-olefin selectivity in the product is good. This method has further promoted the application of transition metal complexes in ethylene oligomerization. In addition, Brookhart reported (Brookhart.M. et al., New Pd(II)-and Ni(II)-Based Catalysts for Polymerization of Ethylene and alpha-Olefins.JACS, 1995, Vol. 117, p. 6414.) A nickel-based catalyst with a diimine structure can prepare linear alpha-olefins by high-activity ethylene oligomerization under the action of MAO. Patent CN1552525A adopts a tridentate nickel-based complex based on a salicylaldimine skeleton to equally show high ethylene oligomerization activity.

[0003] At present, industrialized ethylene oligomerization process mostly adopts homogeneous catalytic system, such as techniques such as Chevron process, BP Amoco process and SHOP.Although above-mentioned commercial homogeneous ethylene oligomerization process has advantages such as good alpha-olefin selectivity and activity height, the product obtained by reaction and catalyst separation difficulty, catalyst waste liquid are difficult to handle unfavorable factors such as recovery, organic solvent usage amount is large, cause homogeneous oligomerization catalyst system use cost higher and its environmental impact is larger.The active component (such as metal organic complex) with good reaction performance in homogeneous catalyst is made to be combined with solid carrier with physical or chemical method, realizes the heterogeneity of catalyst and is supported, is one of the most effective way to address the above problems. On the one hand, the supported catalytic system maintains the advantages of homogeneous catalysts, such as good α-olefin selectivity and high activity, while overcoming the aforementioned shortcomings of homogeneous catalytic systems. On the other hand, it can also inhibit or slow the occurrence of bimolecular deactivation reactions in the catalyst during the reaction, thereby enhancing the stability of the active sites and extending the catalyst life. Furthermore, the presence of the support can reduce the amount of co-catalyst used, increase the specific surface area of ​​the catalyst, increase the number of effective active sites, improve catalytic efficiency, reduce the initial activity of the catalyst, and ensure a smooth release of catalyst activity. Therefore, this type of immobilized catalyst, with its low production cost, environmental friendliness, and the ability to achieve continuous production, has become a very attractive research direction in the field of ethylene oligomerization.

[0004] Xu et al. (Guo CY, Xu H et al., Immobilization of bis(imino)pyridine iron complexes onto mesoporous molecular sieves and their catalytic performance in ethylene oligomerization, Catalysis Communications, 2009, Vol. 10, No. 10, pp. 1467-1471) immobilized bis(imino)pyridine iron complexes onto mesoporous molecular sieves treated with MAO. The supported catalyst exhibited good ethylene oligomerization activity and α-olefin selectivity. When the reaction temperature was low, the oligomerization activity was lower than that of the homogeneous catalyst, but it could still reach 3.2×10 6g / (molFe·h); when the reaction temperature is high, the supported catalyst has far better thermal stability and higher activity than homogeneous catalysts. Furthermore, due to the introduction of the molecular sieve, a "nano-confinement effect" occurs, shifting the carbon number distribution of the generated products toward lower carbon numbers. Furthermore, because the pore size of MCM-41 is smaller than that of SBA-15, it has a stronger confinement effect on macromolecules. Therefore, when MCM-41 is used as a support, the oligomerization product contains more low-molecular-weight α-olefins than when SBA-15 is used as a support, and the α-olefin distribution range is also narrower. However, its selectivity for C4-C8 olefins is not high, and the content of C10 and higher olefins is excessive, exceeding 20%. Braca et al. (Braca G. et al., Organometallic nickel catalysts anchored on polymeric matrices in the oligomerization and / or polymerization of olefins. Part II. Effect and role of the components of the catalytic system. Journal of Molecular Catalysis A: Chemical, 1995, Vol. 96, No. 3, pp. 203-213) prepared a series of supported ethylene oligomerization catalysts by anchoring organonickel bidentate PO chelates onto polystyrene resins via the carbon atoms of the ligands. These supported ethylene oligomerization catalysts can achieve high ethylene oligomerization activity and good α-olefin selectivity.

[0005] Patent CN200510025276.6 uses a new type of diimine nickel or palladium complex for ethylene oligomerization with high catalyst activity and terminal olefin selectivity. Its catalyst activity can reach 2.3×10 6 g / (molNi·h), and the products are mainly C4-C8 olefins, with an α-olefin content greater than 80% and potentially up to 92%. This technology uses an unsupported catalyst, and the catalyst system is homogeneous during polymerization. The catalyst and product cannot be separated or reused.

[0006] Summary of the Invention

[0007] In order to solve the above problems, the present invention aims to provide an organic polymer carrier, an ethylene oligomerization catalyst system, and its preparation method and application. The catalyst system has good ethylene oligomerization activity and α-olefin selectivity and a long service life.

[0008] In order to achieve the above object, the present invention provides an organic polymer carrier, which is obtained by copolymerizing monomers including divinylbenzene and a monomer containing a bidentate pyridine imine ligand;

[0009] Wherein, the monomer containing the bidentate pyridine imine ligand has a structure shown in Formula I:

[0010] In formula I, R1 and R2 are each independently selected from H, halogen, C1-C7 alkyl and its derivatives; R3 is selected from H, halogen, C1-C7 alkyl and its derivatives, C6-C10 aryl and its derivatives; R4 is selected from H, C1-C4 alkyl and its derivatives; x is 0-3 (when x is 0, the vinyl group is directly connected to the pyridine ring).

[0011] According to a specific embodiment of the present invention, preferably, in formula I, R1 and R2 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, and a trifluoromethyl group; R3 is selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a trifluoromethyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a benzyl group; R4 is selected from a hydrogen atom and a methyl group; and x is 0-3.

[0012] According to a specific embodiment of the present invention, preferably, in Formula I, R1 and R2 are each independently selected from a hydrogen atom, a chlorine atom, a bromine atom, and a trifluoromethyl group; R3 is selected from a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, and a trifluoromethyl group; and x is 0 or 1.

[0013] According to a specific embodiment of the present invention, preferably, the monomer containing a bidentate pyridine imine ligand is selected from (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dibromoaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-difluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[( 4-allylpyridin-2-yl)methylene]2,4,6-trichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,4,6-tribromoaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,4,6-trifluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloro-4-methylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dibromo-4 -methylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-difluoro-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]aniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dibromoaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6- Difluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-tribromoaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trifluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dichloro-4-methylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene] Ethylene] 2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene] 2,6-dibromo-4-methylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene] 2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene] 2,6-dibromo-4-tert-butylaniline,6-difluoro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]aniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-difluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,4,6-trichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene] )methylene]2,4,6-tribromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,4,6-trifluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dichloro-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromo-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromo-4-tert-butylaniline, 6-difluoro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dibromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-difluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene] )ethylidene]2,4,6-tribromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,4,6-trifluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dichloro-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dibromo-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-difluoro-4-tert-butylaniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]methylene}aniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]ethylidene}aniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]methylene}2,6-dichloroaniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]ethylidene}2,6-dichloroaniline , (trans)-N-{[4-(allylpentyl)pyridin-2-yl]methylene}aniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]ethylidene}aniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]methylene}2,6-dichloroaniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]ethylidene}2,6-dichloroaniline, or a combination of two or more thereof.

[0014] According to a specific embodiment of the present invention, preferably, the mass fraction of the monomer containing the bidentate pyridine imine ligand is 20-60% based on the mass of the organic polymer carrier as 100%; the content of the functional monomer in the carrier is determined by the added amount of divinylbenzene and the monomer containing the bidentate pyridine imine ligand.

[0015] According to a specific embodiment of the present invention, preferably, the monomer containing the bidentate pyridine imine ligand can be prepared by reacting an aniline compound represented by formula III and a vinyl pyridine compound represented by formula IV.

[0016] Among them, the vinyl pyridine compound represented by Formula IV can be prepared with reference to existing literature (Kitagawa, Kazuya; Inoue, Atsushi; Shinokubo, Hiroshi; Oshima, Koichiro Angewandte Chemie-International Edition, 2000, vol. 39, #14 p. 2481-2483; Furayama, Taniyuki; Yonehara, Mitsuhiro; Arimoto, Sho; Kobayashi, Minoru; Matsumoto, Yotaro; Uchiyama, Masanobu Chemistry-A European Journal, 2008, vol. 14, #33 p. 10348-10356, etc.), for example, by reacting 2-aldehyde (or acetyl)-4-bromopyridine with a brominated unsaturated olefin.

[0017] The present invention also provides a method for preparing the above-mentioned organic polymer carrier, which comprises the following steps: using monomers including divinylbenzene and the monomer containing a bidentate pyridineimine ligand as raw materials, and copolymerizing to obtain the organic polymer carrier; the mass ratio of the monomer containing a bidentate pyridineimine ligand to divinylbenzene is 0.2-2:1.

[0018] According to a specific embodiment of the present invention, preferably, the organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization; the dispersion polymerization method comprises the following steps: adding divinylbenzene and a monomer containing a bidentate pyridine imine ligand to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, reacting at 50-80°C for 5-12 hours, washing, filtering and drying to obtain the organic polymer carrier, which is recorded as a POP carrier.

[0019] According to a specific embodiment of the present invention, preferably, the dispersion solvent includes one or a combination of two or more of an alcohol solvent, a fatty acid ester solvent, and tetrahydrofuran.

[0020] According to a specific embodiment of the present invention, preferably, the alcohol solvent includes one or a combination of two or more of ethanol, propanol, isopropanol, and isobutanol.

[0021] According to a specific embodiment of the present invention, preferably, the fatty acid ester solvent includes one or a combination of two or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, n-pentyl acetate, ethyl formate, n-propyl formate, and n-butyl formate.

[0022] According to a specific embodiment of the present invention, preferably, the mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

[0023] According to a specific embodiment of the present invention, preferably, the stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer.

[0024] According to a specific embodiment of the present invention, preferably, the weight average molecular weight of the stabilizer is 1,000-100,000.

[0025] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of the stabilizer added to the total amount of the monomers added is 0.5-3:100.

[0026] According to a specific embodiment of the present invention, preferably, the initiator is azobisisobutyronitrile (AIBN) and / or dibenzoyl peroxide (BPO).

[0027] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of the initiator added to the total amount of the monomers added is 0.5-3:100.

[0028] According to a specific embodiment of the present invention, preferably, the divinylbenzene is pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

[0029] The present invention can also adopt a dispersion polymerization method, firstly preparing an organic polymer carrier POP1 containing a pyridine aldehyde or ketone functional monomer by free radical copolymerization of divinylbenzene and a vinyl pyridine compound represented by formula IV, and then reacting POP1 with an aniline compound represented by formula III to prepare an organic polymer carrier containing a bidentate pyridine imine ligand group. The structure of POP1 is:

[0030] The present invention also provides an ethylene oligomerization catalyst system (POP-NN-M(II) / MAO), which comprises a main catalyst and a co-catalyst; wherein the main catalyst is a complex formed by the above-mentioned organic polymer carrier and the complex metal M, which has the structure shown in Formula II:

[0031] In formula II, M is selected from Fe, Co or Ni, X is a halogen atom; R1 and R2 are each independently selected from H, halogen, C1-C7 alkyl and its derivatives; R3 is selected from H, halogen, C1-C7 alkyl and its derivatives, C6-C10 aryl and its derivatives; R4 is selected from H, C1-C4 alkyl and its derivatives; x is 0-3.

[0032] According to a specific embodiment of the present invention, preferably, the co-catalyst comprises an alkylaluminoxane compound.

[0033] According to a specific embodiment of the present invention, preferably, the co-catalyst is methylaluminoxane.

[0034] According to a specific embodiment of the present invention, preferably, the molar ratio of aluminum in the co-catalyst to M in the main catalyst is 30-300, more preferably 50-150.

[0035] According to a specific embodiment of the present invention, preferably, the ratio of aluminum in the cocatalyst to the organic polymer support is 1 to 12 mmol aluminum / g support, more preferably 3 to 8 mmol aluminum / g support.

[0036] According to a specific embodiment of the present invention, preferably, in the main catalyst, the content of M is 5 micromoles M / g support to 100 micromoles M / g support, more preferably 20 micromoles M / g support to 50 micromoles M / g support.

[0037] The present invention also provides a preparation method for the above-mentioned ethylene polymerization catalyst system, which comprises the following steps: adding the organic polymer carrier to alcohol, then adding the halide of metal M, reacting at 20°C-70°C for 1-5 hours, filtering, washing, and drying to obtain the main catalyst, mixing the main catalyst and the co-catalyst in an inert solvent, reacting at 0°C-50°C for 30-180 minutes, filtering, washing, and drying to obtain the ethylene polymerization catalyst system.

[0038] According to a specific embodiment of the present invention, the above preparation method comprises the following specific steps:

[0039] A POP support containing a bidentate pyridine imine ligand is added to anhydrous ethanol, followed by a metal halide, such as NiCl2, and the reaction is carried out at a temperature between 20°C and 70°C for 1-5 hours. After completion of the reaction, the unreacted metal halide reagent is filtered, washed, and dried to obtain the organic support-supported pyridine imine-containing metal compound POP-NN-M(II). The dried POP-NN-M(II) and alkylaluminoxane are added to an inert solvent, such as toluene, and the temperature is adjusted to 0°C to 50°C. The reaction is carried out for 30-180 minutes. After completion of the reaction, the reaction is filtered, and the product is washed with an inert solvent and dried to obtain the ethylene oligomerization catalyst system POP-NN-M(II) / MAO.

[0040] The present invention also provides the use of the ethylene oligomerization catalyst system in ethylene oligomerization, which comprises the following steps: mixing the ethylene oligomerization catalyst system with a solvent, introducing ethylene to carry out an ethylene oligomerization reaction.

[0041] According to a specific embodiment of the present invention, preferably, the reaction temperature of the ethylene oligomerization is 0-60°C, and the ethylene partial pressure is 0.1-2.0 MPa.

[0042] According to a specific embodiment of the present invention, preferably, the solvent used in the slurry polymerization of ethylene is C5-C 10 A small amount of alkylaluminum such as triethylaluminum can be added to remove trace water in the solvent during ethylene polymerization.

[0043] The organic carrier-supported ethylene oligomerization catalyst system POP-NN-M(II) / MAO in the present invention is obtained by copolymerizing divinylbenzene with a functional monomer containing a bidentate pyridineimine ligand group to obtain a POP carrier with a porous structure containing a bidentate pyridineimine ligand group. Relying on the bidentate pyridineimine ligand on the POP carrier, the Ni, Co, and Fe metal active centers are fixed on the POP carrier, and then the organic carrier-supported POP-NN-M(II) / MAO catalyst solid component is prepared by reacting with a methylaluminoxane co-catalyst. The catalyst has a high ethylene oligomerization activity, which can reach more than 4000kg / mol.M.bar.h, and the C4-C8 olefin content reaches more than 98%, of which the α-C4 olefin content can reach more than 70%, and the α-olefin content can reach more than 80%. In addition, the prepared catalyst has a long service life, and the ethylene oligomerization activity of the catalyst can be maintained at more than 80% of the original after being reused for the third time. The present invention has the following beneficial effects:

[0044] 1. The present invention designs and prepares a POP-NN-M(II) / MAO catalyst solid catalyst component supported on a POP carrier containing a bidentate pyridine imine ligand group. The catalyst system has good catalytic activity and short-chain olefin selectivity for ethylene oligomerization;

[0045] 2. After ethylene polymerization, the POP-NN-M(II) / MAO catalyst system of the present invention has a C4-C8 olefin content of more than 98%, of which the α-C4 olefin content can reach more than 70%, and the α-olefin content can reach more than 80%. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 is a H NMR spectrum of compound L1-1;

[0047] Figure 2 is a H NMR spectrum of compound L1-3;

[0048] Figure 3 is the H NMR spectrum of compound L1-4. DETAILED DESCRIPTION

[0049] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0050] The monomer used in the carrier preparation process of the present invention is a commercially available monomer of divinylbenzene (DVB), which can be a 55% or 80% DVB content. The monomer requires pretreatment before use to remove the polymerization inhibitor. The inhibitor removal can be performed according to conventional techniques, such as washing with sodium hydroxide solution and distilled water, followed by drying with anhydrous magnesium sulfate.

[0051] The specific surface area of ​​the organic polymer carrier prepared in the present invention was tested using the BET nitrogen adsorption method using Nova 2000e. The specific surface area of ​​the carrier prepared below is greater than 100 m 2 / g, 100-600m 2 / g, and the pore volume is greater than 0.2ml / g.

[0052] Evaluation and analysis method: Gas chromatography GC was used to determine the composition of the oligomers. 1 HNMR test component specific content.

[0053] Example 1

[0054] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0055] 1. Preparation of (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline (L1-1, structure as follows) functional monomer:

[0056] (1) Preparation of 2-formaldehyde-4-allylpyridine (L3-1)

[0057] Reference (Kitagawa, Kazuya; Inoue, Atsushi; Shinokubo, Hiroshi; Oshima, Koichiro Angewandte Chemie-International Edition, 2000, vol. 39, #14 p. 2481-2483.) 2-formaldehyde-4-allylpyridine (L3-1) compound was prepared by reacting 2-formyl-4-bromopyridine with allyl bromide: 100 ml of dried tetrahydrofuran (THF) and 30 mmol of 2-formaldehyde-4-bromopyridine (or 4-bromopyridine-2-carboxaldehyde, CAS: 131747-63-2, molecular weight: 186.01) were added to a 250 ml reaction flask, the reaction temperature was adjusted to -78 ° C, and then 30 mmol of isopropyldi-n-butylmagnesium lithium (iPrBu2MgLi) reagent was added (iPrBu2MgLi reagent can be obtained by 1 mol iPrMgBr (THF solution) was contacted with a Grignard reagent (2 mol BuLi (THF solution)) and reacted for 1 hour to obtain 2-formaldehyde-4-di-n-butylmagnesium-pyridine anion. A slightly excessive amount of 32 mmol allyl bromide and 0.1 g CuCN.2LiCl were then added, stirred and reacted at -78°C for 1 hour. The mixture was filtered and recrystallized to obtain 2-formaldehyde-4-allylpyridine (L3-1) in an 83% yield.

[0058] (2) Preparation of (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline (L1-1) functional monomer:

[0059] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 20 mmol of 2-formaldehyde-4-allylpyridine (L3-1), 20 mmol of aniline (CAS: 62-53-3) and 0.2 g of trifluoroacetic acid were added. The mixture was reacted at 60°C for 1 hour, filtered, and recrystallized from diethyl ether to obtain (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline (L1-1) in an 85% yield.

[0060] L1-1 1 HNMR spectrum: δ7.52, δ7.38 (CH,2-pyridine in DMSO); δ8.84, δ8.59, (CH,2-pyridine in DMSO); δ7.92, δ7.38 (CH,2-pyridine, in DMSO) DMSO); δ7.50, δ7.50 (CH, aldimine); δ7.3, δ7.26 (CH, 1-benzene); δ7.3, δ7.26 (CH, 1-benzene); δ3.22, δ1.37 (CH2, methylene); δ5.70, δ5.25(H,1-ethylene); δ5.03, δ5.25(H,1-ethylene); δ4.97, δ5.25(H,1-ethylene).], as shown in Figure 1.

[0061] 2. Preparation of organic polymer carrier:

[0062] In a 250ml reactor, 130ml of anhydrous ethanol and 10ml of tetrahydrofuran were added, followed by 5.0g of divinylbenzene (Aladdin reagent, 80%) and 3.0g of (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline (L1-1). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% monomer weight of polyvinyl alcohol (PVA, DP 1750). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% monomer weight of AIBN. The reaction was heated to 70°C and allowed to react for 3 hours at a speed of 450 rpm. The reaction was then heated to 80°C and allowed to react for 8 hours. The mixture was filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 5.4g of a free-flowing porous support POP-1 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​562m 2 / g, pore volume 0.56ml / g;

[0063] 3. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0064] In a 250 ml reactor, 2 g of the dried porous POP-1 support containing a bidentate pyridineimine ligand was added, along with 100 ml of anhydrous ethanol. The mixture was then heated to 50°C, 0.05 g of nickel dichloride was added, and the mixture was stirred for 3 hours. After filtration, the mixture was washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above and 100 ml of toluene were also added to a 250 ml reactor. The mixture was then heated to 50°C, and 0.65 g of methylaluminoxane (MAO) solid (white MAO powder obtained by draining a 10% MAO toluene solution) was added. The reaction was continued at room temperature (25°C, the same below) for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing brown-red catalyst particles, designated Cat-1. The catalyst contained 35 μmol / g nickel and 4.5 mmol / g aluminum.

[0065] Example 2

[0066] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0067] In a 250ml reactor, 2g of the dried porous POP-1 support containing a bidentate pyridineimine ligand was added, followed by 100ml of anhydrous ethanol and stirring. The mixture was then heated to 70°C, and 0.05g of cobalt dichloride was added. The mixture was stirred for 2 hours, filtered, washed three times with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Co(II) containing a bidentate pyridineimine ligand. The POP-NN-Co(II) solid catalyst obtained above was added to a 250ml reactor, along with 100ml of toluene and 0.65g of solid methylaluminoxane (MAO). The reaction was then heated to 30°C and allowed to react for 2 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-2. The catalyst contained 31.2 μmol / g of cobalt and 4.7 mmol / g of aluminum.

[0068] Example 3

[0069] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0070] 1. Preparation of an organic polymer support: In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline (L1-1). The mixture was stirred at room temperature for 5 min, followed by the addition of 2% by weight of polyvinyl alcohol (PVA, DP 1750). The mixture was stirred at 45°C for 1 h, followed by the addition of 2.0% by weight of AIBN. The reaction was heated to 70°C and allowed to react for 3 h at 450 rpm. The reaction was then heated to 80°C and allowed to react for 8 h. The mixture was filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 5.2 g of a free-flowing porous support POP-2 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​482 m 2 / g, pore volume 0.45ml / g;

[0071] 2. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0072] In a 250ml reactor, 100ml of anhydrous ethanol and 2g of the dried porous POP-2 support containing a bidentate pyridineimine ligand were added, stirred, and then heated to 50°C. 0.06g of nickel dichloride was added, stirred for 2 hours, filtered, washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was added to a 250ml reactor, along with 100ml of toluene and 0.60g of solid methylaluminoxane (MAO). The reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-3. The catalyst contained 27.5 μmol / g nickel and 4.2 mmol / g aluminum.

[0073] Example 4

[0074] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0075] 1. Preparation of (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloroaniline (L1-2, structure as follows) functional monomer:

[0076] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 20 mmol of 2-formaldehyde-4-allylpyridine (L3-1), and then 20 mmol of 2,6-dichloroaniline (CAS: 608-31-1) were added. 0.2 g of trifluoroacetic acid was added, and the mixture was reacted at 60°C for 1 hour. The mixture was filtered and recrystallized to obtain (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloroaniline (L1-2) in an 88% yield.

[0077] 2. Preparation of organic polymer carrier:

[0078] In a 250ml reactor, 130ml of anhydrous ethanol was added, followed by 5.0g of divinylbenzene (Aladdin reagent, 80%) and 2.5g of (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloroaniline (L1-2). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% by weight of AIBN. The reaction was heated to 80°C and allowed to react for 3 hours at 450 rpm. The reaction was then raised to 80°C and allowed to react for 6 hours. The mixture was filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 5.6g of a free-flowing porous support POP-3 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​387m2. 2 / g, pore volume 0.41ml / g;

[0079] 3. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0080] In a 250ml reactor, 2g of the dried porous POP-3 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. The mixture was then heated to 40°C and 0.06g of nickel dichloride was added. The mixture was stirred for 2 hours, filtered, washed three times with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.70g of solid methylaluminoxane (MAO). The mixture was allowed to react at room temperature for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-4. The catalyst contained 32 μmol / g nickel and 5.2 mmol / g aluminum.

[0081] Example 5

[0082] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0083] 1. Preparation of organic polymer carrier:

[0084] In a 250ml reactor, 130ml of anhydrous ethanol was added, followed by 5.0g of divinylbenzene (Aladdin reagent, 55%) and 2.5g of (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloroaniline (L1-2). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% by weight of AIBN. The reaction was heated to 80°C and allowed to react for 3 hours at 450 rpm. The reaction was then continued at 80°C for 5 hours, filtered, washed three times with anhydrous ethanol, filtered, and dried to yield 4.3g of a free-flowing porous support POP-4 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​257m2. 2 / g, pore volume 0.26ml / g;

[0085] 2. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0086] In a 250ml reactor, 2g of the dried porous POP-4 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. Subsequently, 0.06g of nickel dichloride was added at 35°C and stirred for 3 hours. After filtration, the mixture was washed three times with anhydrous ethanol and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.65g of solid methylaluminoxane (MAO). The mixture was allowed to react at room temperature for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-5. The catalyst contained 28 micromoles of nickel per gram of catalyst and 4.5 mmoles of aluminum per gram of catalyst.

[0087] Example 6

[0088] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0089] 1. Preparation of (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloro-4-trifluoromethylaniline (L1-3, structure as follows) functional monomer:

[0090] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 20 mmol of 2-formaldehyde-4-allylpyridine (L3-1), and then 20 mmol of 2,6-dichloro-4-trifluoromethylaniline (CAS: 24279-39-8) were added. 0.2 g of trifluoroacetic acid was added, and the mixture was reacted at 60°C for 1 hour. The mixture was filtered and recrystallized to obtain (trans)-N-[(4-allylpyridin-2-yl)methylene]-2,6-dichloro-4-trifluoromethylaniline (L1-3) in an 87% yield. The H NMR spectrum is shown in Figure 2.

[0091] 2. Preparation of organic polymer carrier:

[0092] In a 250ml reactor, 130ml of isobutanol was added, followed by 5.0g of divinylbenzene (Aladdin reagent, 80%) and 2.0g of (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloro-4-trifluoromethylaniline (L1-3). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% by weight of AIBN. The reaction was heated to 80°C and allowed to react for 3 hours at 450 rpm. The reaction was then raised to 80°C and allowed to react for 6 hours. The mixture was filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 5.2g of a free-flowing porous support POP-5 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​328m2. 2 / g, pore volume 0.37ml / g;

[0093] 3. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0094] In a 250ml reactor, 2g of the dried porous POP-5 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. 0.065g of nickel dichloride was then added at room temperature and stirred for 5 hours. After filtration, the mixture was washed twice with anhydrous ethanol and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.70g of solid methylaluminoxane (MAO). The reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-6. The catalyst contained 31 μmol / g nickel and 5.0 mmol / g aluminum.

[0095] Example 7

[0096] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0097] In a 250ml reactor, 2g of the dried porous POP-5 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. Then, 0.05g of ferric chloride was added at 60°C and stirred for 2 hours. After filtration, the mixture was washed twice with anhydrous ethanol and dried to obtain the metal compound POP-NN-Fe(II) containing a bidentate pyridineimine ligand. The POP-NN-Fe(II) solid catalyst obtained above was added to a 250ml reactor. The reaction was then heated to 40°C, 100ml of toluene was added, and 0.50g of solid methylaluminoxane (MAO) was added. The reaction was allowed to proceed for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-7. The catalyst contained 25 μmol / g iron and 4.2 mmol / g aluminum.

[0098] Example 8

[0099] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0100] 1. Preparation of (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline (L1-4, structure as follows) functional monomer:

[0101] (1) Preparation of 2-acetyl-4-allylpyridine (L3-2)

[0102] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF) and 30 mmol of 2-acetyl-4-bromopyridine (CAS: 1060805-69-7) were added. The reaction temperature was adjusted to -78°C, and then 30 mmol of isopropyldi-n-butylmagnesium lithium (iPrBu2MgLi) reagent was added. (iPrBu2MgLi reagent can be prepared by contacting 1 mol of iPrMgBr (THF solution) with a Grignard reagent and 2 mol of BuLi (THF solution)) was added. The reaction was allowed to react for 1 hour to prepare 2-acetyl-4-di-n-butylmagnesium-pyridinium anion. Then, a slightly excess of 32 mmol of allyl bromide and 0.1 g of CuCN.2LiCl were added. The reaction was stirred at -78°C for 1 hour, filtered, and recrystallized to obtain 2-acetyl-4-allylpyridine (L3-2) in an 81% yield.

[0103] (2) Preparation of (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline (L1-4) functional monomer

[0104] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 20 mmol of 2-acetyl-4-allylpyridine (L3-2), 20 mmol of 2,4,6-trichloroaniline (CAS: 634-93-5) and 0.2 g of trifluoroacetic acid were added. The mixture was reacted at 60°C for 1 hour, filtered, and recrystallized to obtain (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline (L1-4) in an 83% yield. The H NMR spectrum is shown in Figure 3.

[0105] 2. Organic polymer carrier:

[0106] In a 250 ml reactor, 120 ml of anhydrous ethanol and 20 ml of THF were added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline (L1-4). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% of the monomer weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% of the monomer weight of AIBN. The reaction was heated to 80°C and allowed to react for 3 hours at a speed of 450 rpm. The reaction was then continued to 80°C for 6 hours, filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 4.8 g of a free-flowing porous support POP-6 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​562 m 2 / g, pore volume 0.61ml / g;

[0107] 3. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0108] In a 250ml reactor, 2g of the dried porous POP-6 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. The mixture was then heated to 50°C and 0.065g of nickel dichloride was added. The mixture was stirred for 2 hours, filtered, washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.70g of solid methylaluminoxane (MAO). The mixture was allowed to react at room temperature for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-8. The catalyst contained 35 μmol / g nickel and 5.6 mmol / g aluminum.

[0109] Example 9

[0110] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0111] 1. Preparation of organic polymer carrier:

[0112] In a 250 ml reactor, 130 ml of ethyl acetate was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline (L1-4). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% of the monomer weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% of the monomer weight of AIBN. The reaction was heated to 78°C and allowed to react for 3 hours at a speed of 450 rpm. The reaction was then heated to 80°C and allowed to react for 4 hours. The mixture was filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 5.1 g of a free-flowing porous carrier POP-7 containing a bidentate pyridine imine ligand. The carrier had a specific surface area of ​​378 m 2 / g, pore volume 0.76ml / g;

[0113] 2. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0114] In a 250ml reactor, 2g of the dried porous POP-7 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. The mixture was then heated to 50°C and 0.065g of nickel dichloride was added. The mixture was stirred for 3 hours, filtered, washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.70g of solid methylaluminoxane (MAO). The mixture was allowed to react at room temperature for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-9. The catalyst contained 32 μmol / g nickel and 5.2 mmol / g aluminum.

[0115] Example 10

[0116] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0117] In a 250ml reactor, 2g of dried porous POP-7 support containing a bidentate pyridineimine ligand was added, followed by 100ml of anhydrous ethanol and stirring. The mixture was then heated to 50°C, 0.05g of cobalt dichloride was added, and the mixture was stirred for 2 hours. After filtration, the mixture was washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Co(II) containing a bidentate pyridineimine ligand. The POP-NN-Co(II) solid catalyst obtained above was added to a 250ml reactor. The mixture was then heated to 40°C, 100ml of toluene was added, and 0.60g of solid methylaluminoxane (MAO) was added. The reaction was allowed to proceed for 2 hours. After completion of the reaction, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-10. The catalyst contained 28 μmol / g of cobalt and 4.9 mmol / g of aluminum.

[0118] Example 11

[0119] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0120] 1. Preparation of (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline (L1-5, structure as follows) functional monomer:

[0121] (1) Preparation of 2-acetyl-4-vinylpyridine (L3-3)

[0122] To a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF) and 30 mmol of 2-acetyl-4-bromopyridine (CAS: 1060805-69-7) were added. The reaction temperature was adjusted to -78°C, and then 30 mmol of isopropyldi-n-butylmagnesium lithium (iPrBu2MgLi) reagent was added. [(iPrBu2MgLi reagent can be prepared by contacting 1 mol of iPrMgBr (THF solution) with a Grignard reagent and 2 mol of BuLi (THF solution)] was added. The reaction was allowed to proceed for 1 hour to prepare 2-acetyl-4-di-n-butylmagnesium-pyridinium anion. Then, a slightly excess of 32 mmol of vinyl bromide (CAS No.: 593-60-2) and 0.1 g of CuCN.2LiCl were added. The reaction was stirred at -78°C for 1 hour, filtered, and recrystallized to obtain 2-acetyl-4-vinylpyridine (L3-3) compound in a yield of 78%.

[0123] (2) Preparation of (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline (L1-5) functional monomer:

[0124] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 20 mmol of 2-acetyl-4-vinylpyridine (L3-3), 20 mmol of aniline (CAS: 62-53-3) and 0.2 g of trifluoroacetic acid were added. The mixture was reacted at 60°C for 1 hour, filtered, and recrystallized to obtain (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline (L1-5) in an 82% yield.

[0125] 2. Preparation of organic polymer carrier:

[0126] In a 250ml reactor, 120ml of anhydrous ethanol and 20ml of THF were added, followed by 5.0g of divinylbenzene (Aladdin reagent, 80%) and 2.5g of (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline (L1-5). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% by weight of AIBN. The reaction was heated to 80°C and allowed to react for 3 hours at 450 rpm. The reaction was then raised to 80°C and allowed to react for 6 hours. The mixture was filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 5.1g of a free-flowing porous support POP-8 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​487m2. 2 / g, pore volume 0.52ml / g.

[0127] 3. Preparation of POP-NN-Ni(II) / MAO catalyst:

[0128] In a 250ml reactor, 2g of dried porous POP-8 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. The mixture was then heated to 50°C and 0.065g of nickel dichloride was added. The mixture was stirred for 3 hours, filtered, washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Ni(II) containing a bidentate pyridineimine ligand. The POP-NN-Ni(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.70g of solid methylaluminoxane (MAO). The reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-11. The catalyst contained 32 μmol / g nickel and 5.3 mmol / g aluminum.

[0129] Example 12

[0130] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0131] 1. Preparation of an organic polymer support: In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 55%) and 2.0 g of (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline (L1-5). The mixture was stirred at room temperature for 5 minutes, followed by the addition of 2% by weight of polypropylene oxide-polyethylene oxide copolymer F127 (BASF, molecular weight 12,000). The mixture was stirred at 45°C for 1 hour, followed by the addition of 2.0% by weight of AIBN. The reaction was heated to 80°C and allowed to react for 3 hours at a speed of 450 rpm. The reaction was then continued at 80°C for 5 hours, filtered, washed three times with anhydrous ethanol, filtered, and dried to obtain 4.5 g of a free-flowing porous support POP-9 containing a bidentate pyridine imine ligand. The support had a specific surface area of ​​183 m 2 / g, pore volume 0.22ml / g;

[0132] 2. Preparation of POP-NN-Fe(II) / MAO catalyst:

[0133] In a 250ml reactor, 2g of dried porous POP-9 support containing a bidentate pyridineimine ligand was added, along with 100ml of anhydrous ethanol and stirred. The mixture was then heated to 70°C and 0.065g of ferrous chloride was added. The mixture was stirred for 3 hours, filtered, washed twice with anhydrous ethanol, and dried to obtain the metal compound POP-NN-Fe(II) containing a bidentate pyridineimine ligand. The POP-NN-Fe(II) solid catalyst obtained above was also added to a 250ml reactor, along with 100ml of toluene and 0.70g of solid methylaluminoxane (MAO). The reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the catalyst was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-12. The catalyst contained 35 μmol / g iron and 5.6 mmol / g aluminum.

[0134] Comparative Example 1

[0135] This comparative example provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0136] (1) Preparation of (trans)-N-[(pyridin-2-yl)ethylidene]aniline:

[0137] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 20 mmol of 2-acetylpyridine (CAS: 1122-62-9, Aladdin reagent) and 20 mmol of aniline (CAS: 62-53-3) were added, followed by 0.2 g of trifluoroacetic acid. The mixture was reacted at 60° C. for 1 hour, filtered, and recrystallized to obtain (trans)-N-[(pyridin-2-yl)ethylidene]aniline with a yield of 86%.

[0138] (2) In a 250 ml reactor, 1.0 g of (trans)-N-[(pyridin-2-yl)ethylidene]aniline was added, 100 ml of toluene was added and stirred, then the temperature was raised to 70° C., 0.065 g of nickel dichloride was added, and the mixture was stirred for 3 hours to obtain a toluene solution of a metal compound containing a bidentate pyridine imine ligand NN-Ni(II);

[0139] (3) Preparation of silica gel supported NN-Ni(II) / MAO catalyst:

[0140] In a 250 ml reactor, 2 g of dried Grace 955 silica gel carrier (treated at 600° C. for 6 hours), 100 ml of toluene, and 0.70 g of methylaluminoxane MAO solid were added. The mixture was reacted at room temperature for 2 hours, then the temperature was raised to 70° C., the above-mentioned NN-Ni(II) toluene solution was added, and the mixture was stirred for 3 hours. After the reaction was completed, the mixture was filtered, washed three times with toluene and three times with hexane, and dried to obtain free-flowing catalyst particles, designated Cat-13. The nickel content of the catalyst was 41.5 μmol / g catalyst, and the aluminum content was 6.7 mmol / g catalyst.

[0141] Test Example 1-15: Ethylene oligomerization performance test

[0142] Test Example 1: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of Cat-1 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 30°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.5 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 65.8g of product. The composition of the oligomer was determined by GC, and the main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0143] Test Example 2: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of Cat-2 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 30°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.5 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 43.8g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0144] Test Example 3: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 85mg of Cat-3 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 30°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.8 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 85.6g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0145] Test Example 4: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry hexane and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 82mg of Cat-4 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.8 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 135g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0146] Test Example 5: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of Cat-5 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.8 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 91.8g of product. The composition of the oligomer was determined by GC. The main components were C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0147] Test Example 6: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 65mg of Cat-6 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.6 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 93.4g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0148] Test Example 7: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 55mg of Cat-7 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 1.0 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 78.6g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0149] Test Example 8: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry hexane and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 58mg of Cat-8 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 1.2 MPa and stirred at 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 108.1g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0150] Test Example 9: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of Cat-9 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.8 MPa and stirred at 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 82.3g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0151] Test Example 10: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of Cat-10 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 30°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.5 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 56.5g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0152] Test Example 11: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 10ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of Cat-11 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 30°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.8 MPa and stirred at 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 46.2g of the product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0153] Test Example 12: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry hexane and 10ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 85mg of Cat-12 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.3 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 38.4g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0154] Test Example 13: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, the Cat-6 (R2) ethylene oligomerization catalyst (65 mg) obtained after filtration in Test Example 6 was added for the second time and stirred for 3-5 minutes. The temperature was raised to 60°C, ethylene was introduced, and the pressure was maintained at 0.6 MPa. The reaction was stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 84.1g of the product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1. The ethylene oligomerization activity of the second cycle catalyst Cat-6 was approximately 90% of that of the catalyst in Test Example 6.

[0155] Test Example 14: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, and the stirring speed was 600 rpm. Then, the recycled Cat-6 (denoted as R3) ethylene oligomerization catalyst (65 mg) obtained after filtration in Test Example 13 was added, stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The pressure was maintained at 0.6 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 76.5g of product. The composition of the oligomer was determined by GC. The main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1. The ethylene oligomerization activity of the third cycle was about 81.9% of that of the Cat-6 catalyst in Test Example 6.

[0156] Test Example 15: In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 55mg of Cat-7 (denoted as R2) obtained by filtration in Test Example 7 was added, stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 1.0 MPa and stirred at 600 rpm for 4 hours. After the reaction was completed, the temperature was lowered to obtain 135.3g of product. The composition of the oligomer was determined by GC, and the main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1. The ethylene oligomerization activity was approximately 86% of that of the Cat-7 catalyst in Test Example 7.

[0157] Comparative test example 1:

[0158] In a 2.0L dried ethylene oligomerization reactor, 800ml of dry toluene and 5ml of triethylaluminum TEA (1.0 mol / L) were added, stirred at 600 rpm, and then 80mg of comparative catalyst Cat-13 ethylene oligomerization catalyst was added. The mixture was stirred for 3-5 minutes, heated to 30°C, and ethylene was introduced. The reaction was maintained at a pressure of 0.5 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 17.8g of product. The composition of the oligomer was determined by GC, and the main component was C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR. The results are shown in Table 1.

[0159] Table 1 Ethylene oligomerization results

[0160] From the above polymerization results, it can be seen that the organic carrier-supported ethylene oligomerization catalyst system POP-NN-M(II) / MAO in the present invention has good ethylene oligomerization activity, and its activity can reach above 4000 kg / mol·M·bar·h. The ethylene oligomerization product has good selectivity, and the C4-C8 olefin content reaches above 98%, among which the C4 olefin content can reach above 90%, the α-olefin content can reach above 80%, and the 1-butene content can reach above 75%. In addition, the prepared catalyst has a long service life, and the ethylene oligomerization activity of the catalyst can be maintained at above 80% of the original after the catalyst is reused for the third time.

Claims

1. An organic polymer carrier obtained by copolymerizing monomers comprising divinylbenzene and a monomer containing a bidentate pyridine imine ligand; in, The monomer containing the bidentate pyridine imine ligand has a structure shown in Formula I: In formula I, R1 and R2 are each independently selected from H, halogen, C1-C7 alkyl and its derivatives; R3 is selected from H, halogen, C1-C7 alkyl and its derivatives, C6-C10 aryl and its derivatives; R4 is selected from H, C1-C4 alkyl and its derivatives; x is 0-3.

2. The organic polymer carrier according to claim 1, wherein In formula I, R1 and R2 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, and a trifluoromethyl group; R3 is selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a trifluoromethyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a benzyl group; R4 is selected from a hydrogen atom and a methyl group; and x is 0-3.

3. The organic polymer carrier according to claim 1, wherein In formula I, R1 and R2 are each independently selected from a hydrogen atom, a chlorine atom, a bromine atom, and a trifluoromethyl group; R3 is selected from a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, and a trifluoromethyl group; and x is 0 or 1.

4. The organic polymer carrier according to claim 1, wherein The monomer containing the bidentate pyridine imine ligand is selected from (trans)-N-[(4-allylpyridin-2-yl)methylene]aniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dibromoaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-difluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-difluoroaniline, -N-[(4-allylpyridin-2-yl)methylene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,4,6-trichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,4,6-tribromoaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,4,6-trifluoroaniline, (trans)-N -[(4-allylpyridin-2-yl)methylene]2,6-dichloro-4-methylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dibromo-4-methylaniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-dibromo-4-tert-butylaniline aniline, (trans)-N-[(4-allylpyridin-2-yl)methylene]2,6-difluoro-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]aniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dibromoaniline, (trans)-N-[(4- (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-difluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-tribromoaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trifluoroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dichloro-4-methylaniline, (trans )-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dibromo-4-methylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-allylpyridin-2-yl)ethylidene]2,6-difluoro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]aniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-difluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,4,6-trichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,4,6-tribromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,4,6-trifluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dichloro-4 -methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dichloro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromo-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)methylene]2,6-difluoro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]aniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6 -dibromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-difluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-bis(trifluoromethyl)aniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,4,6-trichloroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,4,6-tribromoaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,4,6-trifluoroaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dichloro-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6- Dichloro-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dibromo-4-methylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-dibromo-4-tert-butylaniline, (trans)-N-[(4-vinylpyridin-2-yl)ethylidene]2,6-difluoro-4-tert-butylaniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]methylene}aniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]ethylidene}aniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]methylene}2,6-dichloroaniline, (trans)-N-{[4-(allylbutyl)pyridin-2-yl]ethylidene}2,6-dichloroaniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]methylene}aniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]ethylidene}aniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]methylene}2,6-dichloroaniline, (trans)-N-{[4-(allylpentyl)pyridin-2-yl]ethylidene}2,6-dichloroaniline, or a combination of two or more thereof.

5. The organic polymer carrier according to claim 1, wherein Calculated based on the mass of the organic polymer carrier being 100%, the mass fraction of the monomer containing the bidentate pyridine imine ligand is 20-60%.

6. The method for preparing the organic polymer carrier according to any one of claims 1 to 5, comprising the following steps: The organic polymer carrier is prepared by copolymerizing monomers including the divinylbenzene and the monomer containing the bidentate pyridine imine ligand as raw materials; The mass ratio of the monomer containing the bidentate pyridine imine ligand to divinylbenzene is 0.2-2:

1.

7. The preparation method according to claim 6, wherein The organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization.

8. The preparation method according to claim 7, wherein The dispersion polymerization method comprises the following steps: adding divinylbenzene and a monomer containing a bidentate pyridine imine ligand into a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80° C. for 5-12 hours to obtain the organic polymer carrier.

9. The preparation method according to claim 8, wherein The dispersing solvent includes one or a combination of two or more of an alcohol solvent, a fatty acid ester solvent, and tetrahydrofuran.

10. The preparation method according to claim 9, wherein The alcohol solvent includes one or a combination of two or more of ethanol, propanol, isopropanol, and isobutanol; The fatty acid ester solvent includes one or a combination of two or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, n-pentyl acetate, ethyl formate, n-propyl formate, and n-butyl formate.

11. The preparation method according to claim 8, wherein The mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

12. The preparation method according to claim 8, wherein The stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer.

13. The preparation method according to claim 12, wherein The weight average molecular weight of the stabilizer is 1,000-100,000.

14. The preparation method according to claim 8, wherein The mass ratio of the amount of the stabilizer added to the total amount of the monomers added is 0.5-3:

100.

15. The preparation method according to claim 8, wherein The initiator is azobisisobutyronitrile and / or dibenzoyl peroxide.

16. The preparation method according to claim 8, wherein The mass ratio of the added amount of the initiator to the total amount of the added monomers is 0.5-3:

100.

17. The preparation method according to claim 6, wherein The divinylbenzene is pretreated divinylbenzene, and the pretreatment is to remove the polymerization inhibitor.

18. An ethylene oligomerization catalyst system comprising a main catalyst and a co-catalyst; in, The main catalyst is a complex formed by the organic polymer carrier complexed with the metal M according to any one of claims 1 to 5, which has a structure shown in Formula II: In formula II, M is selected from Fe, Co or Ni, X is a halogen atom; R1 and R2 are each independently selected from H, halogen, C1-C7 alkyl and its derivatives; R3 is selected from H, halogen, C1-C7 alkyl and its derivatives, C6-C10 aryl and its derivatives; R4 is selected from H, C1-C4 alkyl and its derivatives; x is 0-3.

19. The ethylene oligomerization catalyst system according to claim 18, wherein The cocatalyst includes an alkylaluminoxane compound.

20. The ethylene oligomerization catalyst system according to claim 19, wherein The co-catalyst is methylaluminoxane.

21. The ethylene oligomerization catalyst system according to claim 18, wherein The molar ratio of aluminum in the co-catalyst to M in the main catalyst is 30-300.

22. The ethylene oligomerization catalyst system according to claim 21, wherein The molar ratio of aluminum in the co-catalyst to M in the main catalyst is 50-150.

23. The ethylene oligomerization catalyst system according to claim 18, wherein The ratio of aluminum in the cocatalyst to the organic polymer carrier is 1 mmol aluminum / g carrier to 12 mmol aluminum / g carrier.

24. The ethylene oligomerization catalyst system according to claim 23, wherein The ratio of aluminum in the cocatalyst to the organic polymer carrier is 3 mmol aluminum / g carrier to 8 mmol aluminum / g carrier.

25. The ethylene oligomerization catalyst system according to claim 18, wherein In the main catalyst, the content of M is 5 micromoles M / g support to 100 micromoles M / g support.

26. The ethylene oligomerization catalyst system according to claim 25, wherein In the main catalyst, the content of M is 20 micromoles M / g support to 50 micromoles M / g support.

27. A method for preparing the ethylene oligomerization catalyst system according to any one of claims 18 to 26, comprising the following steps: The organic polymer carrier is added to alcohol, and then the halide of metal M is added, and the reaction is carried out at 20-70°C for 1-5 hours. After filtering, washing and drying, the main catalyst is obtained. The main catalyst and the co-catalyst are mixed in an inert The ethylene oligomerization catalyst system is obtained by reacting the mixture in a solvent at 0° C.-50° C. for 30-180 minutes, filtering, washing and drying.

28. Use of the ethylene oligomerization catalyst system according to any one of claims 18 to 26 in ethylene oligomerization, comprising the following steps: The ethylene oligomerization catalyst system is mixed with a solvent, and ethylene is introduced to carry out ethylene oligomerization reaction.

29. The use according to claim 28, wherein The reaction temperature of the ethylene oligomerization is 0-60° C., and the ethylene partial pressure is 0.1-2.0 MPa.

30. The use according to claim 28, wherein The solvent used in slurry polymerization of ethylene is C5-C 10 of alkanes.

31. The use according to claim 28, wherein The solvent used in the slurry polymerization of ethylene is hexane and / or toluene.

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