Organic polymer carrier, ethylene selective oligomerization catalyst and preparation method and application thereof

Abstract

The invention provides an organic polymer carrier, an ethylene selective oligomerization catalyst and a preparation method and application thereof. The organic polymer carrier is prepared by copolymerizing monomers comprising divinyl benzene and a functional monomer containing a [SO2NCO] group; the functional monomer containing the [SO2NCO] group has a structure as shown in a formula I or a formula II; and the ethylene selective oligomerization catalyst is prepared by loading a Zr compound on the organic polymer carrier. A catalyst system composed of the ethylene selective oligomerization catalyst loaded by the organic polymer carrier and organic aluminum has good catalytic activity and C4-C10 linear alpha-olefin selectivity.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to an organic polymer support, an ethylene selective oligomerization catalyst, its preparation method, and its application. Background Technology

[0002] Ethylene oligomerization is one of the most important methods for producing high-purity α-olefins with even carbon numbers. α-olefins with 4-20 carbon atoms are key raw materials for the production of surfactants, synthetic lubricants, and polyolefin elastomers. For example, 1-hexene, 1-octene, and even higher α-olefins are indispensable comonomers for preparing high-quality and high-performance polyolefins. Traditional ethylene oligomerization catalysis often yields multi-component linear α-olefins with a normal distribution, which can be industrially separated into single components or several mixed components for use as needed. Highly selective ethylene catalysis provides an important pathway for producing single α-olefins with a specific carbon number.

[0003] US3444263A, US3510539A, and US3789081A employ the Ziegler-Natta process with triethylaluminum as a catalyst to produce linear α-olefins. However, the use of large amounts of alkylaluminum as catalysts makes the reaction difficult to control. Subsequently, patent US3644563A, using a phosphonooxy bidentate nickel complex as a catalyst—the well-known SHOP catalyst system—successfully achieved the industrialization of ethylene oligomerization, representing a major breakthrough in the field. The SHOP process offers high activity and good product quality, but the multiple isomerization and disproportionation processes result in a lengthy process and high investment costs. 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) that nickel-based catalysts with diimine structures can achieve highly active ethylene oligomerization to prepare linear α-olefins under MAO conditions. CN1552525A, which uses a tridentate nickel-based complex based on a salicylaldehyde-imine framework, also exhibits high ethylene oligomerization activity.

[0004] Currently, most industrialized ethylene oligomerization processes employ homogeneous catalytic systems, such as the Chevron process, the BP Amoco process, and the SHOP process. While these commercially available homogeneous ethylene oligomerization processes offer advantages such as good α-olefin selectivity and high activity, disadvantages include difficulties in separating the reaction products from the catalyst, challenges in treating and recovering catalyst waste, and large consumption of organic solvents. These factors lead to high operating costs and significant environmental impacts for homogeneous oligomerization catalyst systems. One of the most effective ways to address these problems is to combine the active components with good reactivity (such as organometallic complexes) in the homogeneous catalyst with a solid support using physical or chemical methods, thus achieving catalyst heterogeneity, i.e., loading. The supported catalytic system retains the advantages of homogeneous catalysts, such as high selectivity and activity for α-olefins, while overcoming the aforementioned shortcomings of homogeneous catalytic systems. Furthermore, it inhibits or slows down bimolecular deactivation reactions during the reaction, enhancing the stability of active sites and extending catalyst lifetime. The support also reduces the amount of co-catalyst used, increases the specific surface area of ​​the catalyst, increases effective active sites, improves catalytic efficiency, reduces initial catalyst activity, and allows for a stable release of catalyst activity. Therefore, this type of supported catalyst, characterized by 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.

[0005] US20090306449A1 and US20110054130A1 report the use of a zirconium carbonate complex as the main catalyst for ethylene oligomerization, with the general formula ZrCl. 4-m (R 1 Using organoaluminum as a cocatalyst, preferably a combination of diethylaluminum chloride and an electron donor, or a mixture of diethylaluminum chloride and at least two electron donors, high-purity, low-molecular-weight linear α-olefins are obtained through their synergistic effect. Although the addition of electron donors increases the purity of the linear α-olefin (Al / Zr = 17.5), it reduces the catalyst activity. Furthermore, increasing the Al / Zr molar ratio results in the formation of a large amount of waxy or polymeric components in the system, which not only reduces the yield of low-molecular-weight ethylene oligomers but also affects their purity. US20050070425A1 discloses a dialkyl sulfone compound (R1SO2R2), such as diphenyl sulfone (Ph2SO2), which reacts with titanium, zirconium, and hafnium metal atoms to form a sulfonyl or sulfonic acid-containing metal complex. After reacting with a catalyst of diethylaluminum chloride, it undergoes ethylene oligomerization with a polymerization activity of over 4000 g / gZr·h. The linear α-olefin content of the C4-C8 component can reach over 85%, of which the C6-C8 content can reach over 50%, but the C6-C8 content is still slightly low. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide an organic polymer support, an ethylene selective oligomerization catalyst, its preparation method, and its application. The catalyst system composed of the ethylene selective oligomerization catalyst and organoaluminum exhibits good catalytic activity and C4-C10 linear α-olefin selectivity.

[0007] To achieve the above objectives, the present invention provides an organic polymer carrier, which is obtained by copolymerization of a monomer comprising divinylbenzene and a functional monomer containing a [SO2NCO] group (denoted as monomer L1); wherein the functional monomer containing the [SO2NCO] group has the structure shown in Formula I or Formula II:

[0008]

[0009] In Formula I, R1 is selected from single bonds, C1-C10 hydrocarbon groups and their derivatives; R2 and R3 may be the same or different, and are each independently selected from H, C1-C10 hydrocarbon groups and their derivatives; when R1 is a single bond, it means that the carbon atom connected to R1 is directly bonded to the S atom.

[0010] In Formula II, R1' is selected from single bonds, C1-C10 alkylene groups and their derivatives; R2' and R3' may be the same or different, and are each independently selected from C1-C10 alkylene groups and their derivatives.

[0011] According to a specific embodiment of the present invention, preferably, in Formula I, R1 is selected from single bond, methylene, ethylene, phenylene, and cycloalkylene; R2 and R3 may be the same or different, and are each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, chlorophenyl, and trifluoromethyl; more preferably, R1 is selected from single bond (the carbon atom connected to R1 is directly bonded to the S atom), methylene, and phenylene, and R2 and R3 are each independently selected from methyl, phenyl, isopropyl, and tert-butyl.

[0012] According to a specific embodiment of the present invention, preferably, in Formula II, R1' is selected from a single bond, methylene, ethylene, phenylene, or cycloalkylene; R2' and R3' may be the same or different, and each is independently selected from methylene, ethylene, isopropylene, tert-butylene, phenylene, benzylene, chlorophenylene, or trifluoromethylene; more preferably, R1' is selected from a single bond (the carbon atom connected to R1' is directly bonded to the S atom), methylene, or phenylene, and R2' and R3' are each independently selected from methyl, phenyl, isopropyl, tert-butyl, or the R2' and R3' groups are bonded together to form a pyrrolidone ring.

[0013] According to a specific embodiment of the present invention, preferably, the functional monomer containing the [SO2NCO] group is selected from N-(vinylsulfonyl)-N-methylacetamide, N-(vinylsulfonyl)-N-ethylacetamide, N-(vinylsulfonyl)-N-tert-butylacetamide, N-(vinylsulfonyl)-N-phenylacetamide, N-(vinylsulfonyl)-N-phenylbenzamide, N-(vinylsulfonyl)-benzamide, N-(vinylsulfonyl)-phenylacetamide, N-(vinylsulfonyl)-N-benzylformamide, N-(vinylsulfonyl)-N-benzylacetamide, N-(vinylsulfonyl)-N-phenyl-2-chlorobenzamide, N-(vinylsulfonyl)-N -Trifluoromethylphenylacetamide, N-(allylsulfonyl)-formamide, N-(allylsulfonyl)-acetamide, N-(allylsulfonyl)-N-methylacetamide, N-(allylsulfonyl)-N-ethylacetamide, N-(allylsulfonyl)-N-tert-butylacetamide, N-(allylsulfonyl)-N-phenylformamide, N-(allylsulfonyl)-N-phenylacetamide, N-(allylsulfonyl)-N-phenylbenzamide, N-(allylsulfonyl)-benzamide, N-(allylsulfonyl)-N-phenylacetamide, N-(allylsulfonyl)-N-benzylformamide, N-(allylsulfonyl)-N-benzylacetamide, N-(allylsulfonyl)-N-benzylbenzamide, N-(allylsulfonyl)-N-phenyl- 2-Chlorobenzamide, N-(allylsulfonyl)-N-trifluoromethylphenylacetamide, N-(p-styrenesulfonyl)-formamide, N-(p-styrenesulfonyl)-acetamide, N-(p-styrenesulfonyl)-N-methylacetamide, N-(p-styrenesulfonyl)-N-ethylacetamide, N-(p-styrenesulfonyl)-N-tert-butylacetamide, N-(p-styrenesulfonyl)-N-phenylformamide, N-(p-styrenesulfonyl)-N-phenylacetamide, N-(p-styrenesulfonyl)-N-phenylbenzamide, N-(p-styrenesulfonyl)-benzamide, N-(p-styrenesulfonyl)-phenylacetamide, N-(p-styrenesulfonyl)-N-benzylformamide, N-(p-styrenesulfonyl) -N-Benzylacetamide, N-(p-styrenesulfonyl)-N-Benzylbenzamide, N-(p-styrenesulfonyl)-N-Pheny-2-chlorobenzamide, N-(p-styrenesulfonyl)-N-Trifluoromethylphenylacetamide, N-(1-allylcyclopropanesulfonyl)-formamide, N-(1-allylcyclopropanesulfonyl)-acetamide, N-(1-allylcyclopropanesulfonyl)-N-methylacetamide, N-(1-allylcyclopropanesulfonyl)-N-ethylacetamide, N-(1-allylcyclopropanesulfonyl)-N-tert-butylacetamide, N-(1-allylcyclopropanesulfonyl)-N-phenylformamide, N-(1-allylcyclopropanesulfonyl)-N-phenylacetamide, N-(1-allylcyclopropanesulfonyl)-N-phenylbenzamideN-(1-Allylcyclopropanesulfonyl)-benzamide, N-(1-Allylcyclopropanesulfonyl)-phenylacetamide, N-(1-Allylcyclopropanesulfonyl)-N-benzylacetamide, N-(1-Allylcyclopropanesulfonyl)-N-benzylbenzamide, N-(1-Allylcyclopropanesulfonyl)-N-phenyl-2-chlorobenzamide, N-(1-Allylcyclopropanesulfonyl)-N-trifluoromethylphenylacetamide, 1-(vinylsulfonyl)-2- One or more of the following: pyrrolidone, 1-(allylsulfonyl)-2-pyrrolidone, 1-(p-styrenesulfonyl)-2-pyrrolidone, 1-(1-allylcyclopropanesulfonyl)-2-pyrrolidone, 5-methyl-1-(vinylsulfonyl)-2-pyrrolidone, 5-methyl-1-(allylsulfonyl)-2-pyrrolidone, 5-methyl-1-(p-styrenesulfonyl)-2-pyrrolidone, and 5-methyl-1-(1-allylcyclopropanesulfonyl)-2-pyrrolidone.

[0014] According to a specific embodiment of the present invention, preferably, the mass fraction of the functional monomer containing the [SO2NCO] group is 10-70%, more preferably 20%-60%, calculated based on 100% of the mass of the organic polymer carrier.

[0015] This invention also provides a method for preparing the above-mentioned organic polymer carrier, which includes the following steps: using monomers comprising divinylbenzene and functional monomers containing [SO2NCO] groups as raw materials, the organic polymer carrier (denoted as POP-SNO) is obtained by copolymerization, and the structure of the organic polymer carrier is shown in Formula III or Formula IV:

[0016]

[0017] In Formula III, R1 is selected from single bonds, C1-C10 hydrocarbon groups and their derivatives, such as methylene, ethylene, phenylene, etc. When R1 is a single bond, it means that the carbon atom connected to R1 is directly bonded to the S atom; R2 and R3 may be the same or different, and are each independently selected from H, C1-C10 hydrocarbon groups and their derivatives, such as methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, chlorophenyl, trifluoromethyl;

[0018] In Formula IV, R1' is selected from single bonds, C1-C10 alkylene groups and their derivatives; R2' and R3' may be the same or different, and are each independently selected from C1-C10 alkylene groups and their derivatives.

[0019] According to a specific embodiment of the present invention, preferably, the organic polymer carrier is prepared by free radical polymerization, such as by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization.

[0020] According to a specific embodiment of the present invention, preferably, the dispersion polymerization method includes the following steps: adding divinylbenzene and a functional monomer containing [SO2NCO] groups to a dispersion solvent, then adding a stabilizer and an initiator, reacting at 50-80°C for 5-12 hours, and obtaining the organic polymer carrier after washing, filtering, and drying, denoted as POP-SNO. The content of the functional monomer containing [SO2NCO] groups in the organic polymer carrier is determined by the amount of divinylbenzene and the amount of functional monomer L1 containing [SO2NCO] groups added.

[0021] According to a specific embodiment of the present invention, preferably, the reaction conditions of the dispersion polymerization method satisfy one or more of the following (1)-(8):

[0022] (1) The dispersion solvent includes one or more of alcohols, fatty acid ester solvents, and tetrahydrofuran;

[0023] (2) The total amount of monomer added is 1:5-20 in mass ratio to the dispersing solvent;

[0024] (3) The mass ratio of the functional monomer containing the [SO2NCO] group to divinylbenzene is 0.2-2:1;

[0025] (4) The stabilizer includes polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer;

[0026] (5) The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-3:100;

[0027] (6) The initiator includes azobisisobutyronitrile and / or benzoyl peroxide;

[0028] (7) The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:100;

[0029] (8) The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

[0030] According to a specific embodiment of the present invention, preferably, the alcohol in the dispersion solvent includes, but is not limited to, one or a combination of two or more of ethanol, propanol, isopropanol, and isobutanol.

[0031] According to a specific embodiment of the present invention, preferably, the dispersion solvent is a fatty acid ester solvent including, but not limited to, one 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.

[0032] According to a specific embodiment of the present invention, preferably, the weight-average molecular weight of the stabilizer is 1000-100000.

[0033] According to a specific embodiment of the present invention, preferably, the functional monomer containing the [SO2NCO] group is prepared by reacting a compound containing a sulfonyl chloride [SO2Cl] group (L2) with an amide compound (L3) under alkaline conditions; the general formula of the amide compound L3 is R2NHCOR3, R2 and R3 may be the same or different, and each is independently selected from H, C1-C10 hydrocarbon groups and their derivatives; R2 and R3 can be bonded to form a ring; the general formula of the functional monomer L2 containing the sulfonyl chloride group is CH2=CH-R1-SO2Cl; R1 is selected from single bonds, C1-C10 hydrocarbon groups and their derivatives, when R1 is a single bond, it means that the carbon atom connected to R1 is directly bonded to the S atom, and the structure of L2 is shown in Formula V;

[0034]

[0035] The aforementioned compounds L2 containing sulfonyl chloride groups include, but are not limited to, p-styrenebenzenesulfonate chloride (CAS: 2633-67-2), vinylsulfonyl chloride (CAS: 6608-47-5), allylsulfonyl chloride (CAS: 14418-84-9), and 1-allylcyclopropanesulfonyl chloride (CAS: 923032-59-1). Compound L2 containing sulfonyl chloride groups can be prepared using commercially available monomers or by the following method: p-styrenesulfonyl chloride is synthesized by reacting sodium p-styrenesulfonate with sulfur oxychloride (SOCl2) in N,N-dimethylformamide (DMF) solvent, with a yield of approximately 94%.

[0036] According to a specific embodiment of the present invention, preferably, the synthesis of the functional monomer containing the [SO2NCO] group can be carried out using dichloromethane as a solvent, reacting the corresponding sulfonyl chloride group compound L2 with the corresponding amide compound L3 under alkaline conditions at room temperature (25°C). The bases used include triethylamine, pyridine, 4-dimethylaminopyridine (DMAP), etc., and other stronger bases include potassium hydroxide, potassium tert-butoxide (t-BuOK), and sodium hydride, etc.

[0037] According to a specific embodiment of the present invention, preferably, the sulfonyl chloride-containing compound (L2) and the amide compound (L3) react in a molar ratio of 0.9-1.1:1 (e.g., 1:1).

[0038] The present invention also provides an ethylene selective oligomerization catalyst, which is prepared by supporting Zr compounds on the above-mentioned organic polymer support.

[0039] According to a specific embodiment of the present invention, preferably, the Zr content in the ethylene selective oligomerization catalyst is from 50 micromoles of Zr / g catalyst to 800 micromoles of Zr / g catalyst, more preferably from 200 micromoles of Zr / g catalyst to 500 micromoles of Zr / g catalyst.

[0040] The present invention also provides a method for preparing the above-mentioned ethylene selective oligomerization catalyst, which includes the following steps: reacting the organic polymer support and the zirconium compound precursor in equal amounts in an organic solvent (such as dichloromethane) at 0-40°C for 1-5 h to obtain the ethylene selective oligomerization catalyst, denoted as POP-SNO-Zr.

[0041] According to a specific embodiment of the present invention, preferably, the zirconium compound precursor includes one or a combination of two or more of zirconium tetrachloride, zirconium tetrachlorobistetrahydrofuranide, and chromium trihydrofuranide.

[0042] The present invention also provides an ethylene selective oligomerization catalyst system, which comprises the above-mentioned ethylene selective oligomerization catalyst and an organoaluminum co-catalyst (the organoaluminum co-catalyst is added during the ethylene oligomerization process).

[0043] According to a specific embodiment of the present invention, preferably, the organoaluminum co-catalyst includes one or more of triethylaluminum, triisobutylaluminum, and diethylaluminum chloride, more preferably diethylaluminum chloride; the ethylene selective oligomerization catalyst system using diethylaluminum chloride as a co-catalyst is denoted as POP-SNO-Zr / AlEt2Cl.

[0044] According to a specific embodiment of the present invention, preferably, in the ethylene selective oligomerization catalyst system, the molar ratio of Al to Zr is 1-500, more preferably 5-200.

[0045] The present invention also provides a method for preparing α-olefins by selective oligomerization of ethylene, which uses the above-mentioned selective oligomerization catalyst or the above-mentioned selective oligomerization catalyst system to carry out the ethylene oligomerization reaction, including the following steps: adding solvent and impurity remover to a reaction vessel, then adding the ethylene selective oligomerization catalyst and organoaluminum co-catalyst, mixing and heating, and then introducing ethylene to carry out the reaction to obtain the ethylene oligomerization product.

[0046] According to a specific embodiment of the present invention, preferably, the content of C6-C10 olefin products in the ethylene oligomer is greater than 70%, more preferably greater than 80%.

[0047] According to a specific embodiment of the present invention, preferably, the selectivity (or purity) of linear α-olefins in the C6-C10 olefin products is greater than 95%, more preferably greater than 98%. This selectivity (or purity) is the mass percentage of "linear C6-C10 α-olefins" to "C6-C10 olefins".

[0048] According to a specific embodiment of the present invention, preferably, the temperature of the ethylene oligomerization reaction is 20-80°C and the partial pressure of ethylene is 1-10 MPa.

[0049] According to a specific embodiment of the present invention, preferably, the ethylene oligomerization reaction is a slurry polymerization, and the solvent used includes C5-C10 alkanes, more preferably one or a combination of two or more of hexane, cyclohexane, toluene, and methylcyclohexane, and more preferably methylcyclohexane.

[0050] According to a specific embodiment of the present invention, preferably, a small amount of alkyl aluminum (e.g., triethylaluminum) may be added to the ethylene oligomerization reaction to remove trace amounts of water from the solvent.

[0051] This invention provides an organic polymer support, an ethylene selective oligomerization catalyst, its preparation method, and its application. The invention first copolymerizes a functional monomer containing [SO2NCO] groups with divinylbenzene to obtain a porous organic polymer support (POP-SNO). A zirconium-containing metal compound is then supported on this support to obtain the main catalyst POP-SNO-Zr (i.e., the ethylene selective oligomerization catalyst). The main catalyst and an organoaluminum co-catalyst constitute the ethylene selective oligomerization catalyst system.

[0052] The present invention has the following beneficial effects:

[0053] 1. This invention prepares a solid catalyst POP-SNO-Zr supported on a POP support containing [SO2NCO] groups. The catalyst system formed by POP-SNO-Zr and an organoaluminum catalyst is suitable for the preparation of α-olefins by ethylene oligomerization, especially 1-C6 and 1-C8 linear α-olefins. It has good catalytic activity and C4-C10 linear α-olefin selectivity for ethylene oligomerization.

[0054] 2. The ethylene selective oligomerization catalyst system supported on an organic polymer support of the present invention is used to obtain high content of C6-C10 olefins and high purity of C6-C10 linear α-olefins after ethylene oligomerization. Detailed Implementation

[0055] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0056] Raw material source:

[0057] The monomer divinylbenzene (abbreviated as DVB) used below can be a commercially available monomer with a DVB content of 55% or 80%. Divinylbenzene requires pretreatment before use to remove the polymerization inhibitor. The method for removing the polymerization inhibitor can be carried out according to existing technology. For example, divinylbenzene can be washed with sodium hydroxide solution and distilled water, and then dried with anhydrous magnesium sulfate before use.

[0058] Evaluation and analysis methods: The composition of the oligomers was determined by gas chromatography (GC). 1 HNMR was used to determine the specific content of the components. Elemental analysis (PerkinElmer 2400II) was used to verify the synthesis of the monomers.

[0059] Example 1

[0060] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0061] (1) Preparation of N-(vinylsulfonyl)-N-methylacetamide (L1-1) functional monomer:

[0062]

[0063] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of vinylsulfonyl chloride (CAS: 6608-47-5) reagent, then 42 mmol of N-methylacetamide (CAS: 79-16-3) and 50 mmol of triethylamine. The reaction was carried out at room temperature for 1 hour, filtered, and recrystallized from dichloromethane to prepare N-(vinylsulfonyl)-N-methylacetamide (L1-1) with a yield of 93%. Elemental analysis: C, 36.8%; H, 5.6%; N, 8.6%; O, 29.4%; S, 19.6%.

[0064] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0065] In a reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (80%) and 3.0 g of N-(vinylsulfonyl)-N-methylacetamide (L1-1). The mixture was stirred at room temperature for 5 min, and then 2.0% of polyvinyl alcohol (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, followed by 2.0% of AIBN. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a speed of 450 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 6 h. After filtration, the mixture was washed three times with anhydrous ethanol. After filtration and drying, 4.7 g of free-flowing porous organic polymer carrier POP-SNO-1 containing [SO2NCO] groups was obtained.

[0066] (3) Preparation of POP-SNO-Zr catalyst:

[0067] In a reactor, 2.0 g of dried porous POP-SNO-1 support containing [SO2NCO] groups was added, along with 1.28 mmol (approximately 0.3 g) of zirconium tetrachloride (CAS: 12331-30-5). The mixture was stirred at room temperature (25℃, the same below) for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed twice with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-1. The zirconium content in catalyst Cat-1 was 387 μmol / g catalyst.

[0068] Example 2

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

[0070] (1) Preparation of N-(vinylsulfonyl)-N-methylbenzamide (L1-2) functional monomer:

[0071]

[0072] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of vinylsulfonyl chloride (CAS: 6608-47-5) reagent, then 42 mmol of N-methylbenzamide (CAS: 613-93-4) and 50 mmol of triethylamine. The reaction was carried out at room temperature for 2 hours, filtered, and recrystallized from dichloromethane to prepare N-(vinylsulfonyl)-N-methylbenzamide (L1-2) with a yield of 95%. Elemental analysis: C, 53.3%; H, 4.9%; N, 6.2%; O, 21.4%; S, 14.2%.

[0073] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0074] In a reactor, 130 ml of anhydrous ethanol and 10 ml of tetrahydrofuran were added, followed by 5.0 g of divinylbenzene (80%) and 3.0 g of N-(vinylsulfonyl)-N-methylbenzamide (L1-2). The mixture was stirred at room temperature for 5 min, and then 2% of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of AIBN was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a speed of 450 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 6 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 5.1 g of free-flowing porous organic polymer carrier POP-SNO-2 containing [SO2NCO] groups.

[0075] (3) Preparation of POP-SNO-Zr catalyst:

[0076] In a reactor, 2.0 g of dried porous POP-SNO-2 support containing [SO2NCO] groups was added, along with 1.28 mmol (approximately 0.3 g) of zirconium tetrachloride. The mixture was stirred at 40 °C for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed twice with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-2. The zirconium content in catalyst Cat-2 was 415 μmol / g catalyst.

[0077] Example 3

[0078] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0079] (1) Preparation of N-(allylsulfonyl)-N-methylbenzamide (L1-3) functional monomer:

[0080]

[0081] Allyl sulfonyl chloride (CAS: 14418-84-9) can be prepared according to the literature "Kamogawa, Hiroyoshi; Kanzawa, Asami; Kadoya, Masahiro; Naito, Takeshi; Nanasawa, Masato. Bulletin of the Chemical Society of Japan, 1983, Vol. 56, No. 3, pp. 762-765."

[0082] In a reactor, 100 ml of dried N,N-dimethylformamide (DMF) solvent was added, followed by 40 mmol of sodium allyl sulfonate (CAS: 2495-39-8), and then 42 mmol of sulfur oxychloride (SOCl2). The reaction was carried out at room temperature for 1-2 hours, filtered, and washed twice with dichloromethane to obtain allyl sulfonyl chloride with a yield of approximately 94%.

[0083] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of commercially available or synthetic allyl sulfonyl chloride (CAS: 14418-84-9) reagent, then 42 mmol of N-methylbenzamide (CAS: 613-93-4) and 50 mmol of triethylamine. The reaction was carried out at room temperature for 2 hours, filtered, and recrystallized from dichloromethane to prepare N-(allyl sulfonyl)-N-methylbenzamide (L1-3), with a yield of 96%. Elemental analysis: C, 55.2%; H, 5.5%; N, 5.8%; O, 20.1%; S, 13.4%.

[0084] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0085] In a reactor, 130 ml of anhydrous ethanol and 10 ml of tetrahydrofuran were added, followed by 5.0 g of divinylbenzene (80%) and 3.0 g of N-(allylsulfonyl)-N-methylbenzamide (L1-3). The mixture was stirred at room temperature for 5 min, and then 2% of the total monomer mass of F127 (BASF commercially available polypropylene oxide-ethylene oxide copolymer, molecular weight approximately 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of the total monomer mass of AIBN was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a rotation speed of 350 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 5 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.8 g of free-flowing porous organic polymer carrier POP-SNO-3 containing [SO2NCO] groups.

[0086] (3) Preparation of POP-SNO-Zr catalyst:

[0087] In a reactor, 2.0 g of dried porous POP-SNO-3 support containing [SO2NCO] groups was added, along with 1.28 mmol (approximately 0.3 g) of zirconium tetrachloride. The mixture was stirred at room temperature for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed twice with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-3. The zirconium content in catalyst Cat-3 was 423 μmol / g catalyst.

[0088] Example 4

[0089] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0090] (1) Preparation of N-(p-styrenesulfonyl)-N-methylbenzamide (L1-4) functional monomer:

[0091]

[0092] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of commercially available or synthetic p-styrenesulfonyl chloride (CAS: 2633-67-2), then 42 mmol of N-methylbenzamide (CAS: 613-93-4) and 50 mmol of triethylamine. The reaction was carried out at room temperature for 1 hour, filtered, and recrystallized from dichloromethane to prepare N-(p-styrenesulfonyl)-N-methylbenzamide (L1-4), with a yield of 93%. Elemental Analysis: C, 63.8%; H, 5.0%; N, 4.7%; O, 15.9%; S, 10.6%.

[0093] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0094] In a reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (80%) and 2.0 g of N-(p-styrenesulfonyl)-N-methylbenzamide (L1-4). The mixture was stirred at room temperature for 5 min, and then 2% of the total monomer mass of F127 (BASF commercially available polypropylene oxide-ethylene oxide copolymer, molecular weight approximately 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of the total monomer mass of AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 6 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.1 g of free-flowing porous organic polymer carrier POP-SNO-4 containing [SO2NCO] groups.

[0095] (3) Preparation of POP-SNO-Zr catalyst:

[0096] In a reactor, 2.0 g of dried porous POP-SNO-4 support containing [SO2NCO] groups was added, along with 1.0 mmol (0.24 g) of zirconium tetrachloride. The mixture was stirred at 40 °C for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-4. The zirconium content in catalyst Cat-4 was 392 μmol / g catalyst.

[0097] Example 5

[0098] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0099] In a reactor, 2.0 g of dried porous POP-SNO-4 support containing [SO2NCO] groups was added, along with 1.0 mmol (0.377 g) of tetrachlorobis(tetrahydrofuran)zirconia ZrCl4(THF)2 (CAS: 21959-01-3). The mixture was stirred at room temperature for 3 hours, then 100 ml of dichloromethane was added and stirred for 0.5 hours. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-5. The zirconium content in catalyst Cat-5 was 354 μmol / g catalyst.

[0100] Example 6

[0101] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0102] (1) Preparation of N-(p-styrenesulfonyl)-N-phenyl-2-chlorobenzamide (L1-5):

[0103]

[0104] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of commercially available or synthetic p-styrenesulfonyl chloride (CAS: 2633-67-2), then 42 mmol of N-phenyl-2-chlorobenzamide (CAS: 6833-13-2) and 50 mmol of triethylamine. The reaction was carried out at room temperature for 2 hours. After filtration, the product was recrystallized from dichloromethane to prepare N-(p-styrenesulfonyl)-N-phenyl-2-chlorobenzamide (L1-5), with a yield of 91%. Elemental Analysis: C, 63.4%; H, 4.0%; Cl, ​​8.9%; N, 3.5%; O, 12.1%; S, 8.1%.

[0105] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0106] In a reactor, 130 ml of anhydrous ethanol and 20 ml of tetrahydrofuran were added, followed by 5.0 g of divinylbenzene (80%) and 2.5 g of N-(p-styrenesulfonyl)-N-phenyl-2-chlorobenzamide (L1-5). The mixture was stirred at room temperature for 5 min, and then 2% of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of benzoyl peroxide (BPO) was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a speed of 450 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 10 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 5.4 g of free-flowing porous organic polymer carrier POP-SNO-5 containing [SO2NCO] groups.

[0107] (3) Preparation of POP-SNO-Zr catalyst:

[0108] In a reactor, 2.0 g of dried porous POP-SNO-5 support containing [SO2NCO] groups was added, along with 1.0 mmol (approximately 0.24 g) of zirconium tetrachloride. The mixture was stirred at room temperature for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed twice with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-6. The zirconium content in catalyst Cat-6 was 375 μmol / g catalyst.

[0109] Example 7

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

[0111] In a reactor, 2.0 g of dried porous POP-SNO-5 support containing [SO2NCO] groups was added, along with 1.0 mmol (0.377 g) of tetrachlorobistetrahydrofuranized zirconium ZrCl4(THF)2 (CAS: 21959-01-3). The mixture was stirred at room temperature for 3 hours, then 100 ml of dichloromethane was added and stirred for 0.5 hours. After filtration, the mixture was washed twice with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-7. The zirconium content in catalyst Cat-7 was 318 μmol / g catalyst.

[0112] Example 8

[0113] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0114] (1) Preparation of N-(1-allylcyclopropanesulfonyl)-N-ethylacetamide:

[0115]

[0116] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of commercially available or synthetic 1-allylcyclopropanesulfonyl chloride (CAS: 923032-59-1), then 42 mmol of N-ethylacetamide (CAS: 625-50-3) and 50 mmol of triethylamine. The reaction was carried out at room temperature for 3 hours, filtered, and recrystallized from dichloromethane to prepare N-(1-allylcyclopropanesulfonyl)-N-ethylacetamide (L1-6), with a yield of 91%. Elemental analysis: C, 51.9%; H, 7.4%; N, 6.1%; O, 20.7%; S, 13.9%.

[0117] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0118] In a reactor, 130 ml of anhydrous ethanol and 13 ml of ethyl acetate were added, followed by 5.0 g of divinylbenzene (80%) and 3.0 g of N-(1-allylcyclopropanesulfonyl)-N-ethylacetamide (L1-6). The mixture was stirred at room temperature for 5 min, and then 2% of the total monomer mass of F127 (BASF commercially available polypropylene oxide-ethylene oxide copolymer, molecular weight approximately 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of the total monomer mass of benzoyl peroxide (BPO) was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a rotation speed of 350 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 10 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.5 g of free-flowing porous organic polymer carrier POP-SNO-6 containing [SO2NCO] groups.

[0119] (3) Preparation of POP-SNO-Zr catalyst:

[0120] In a reactor, 2.0 g of dried porous POP-SNO-6 support containing [SO2NCO] groups was added, along with 1.28 mmol (approximately 0.3 g) of zirconium tetrachloride. The mixture was stirred at room temperature for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-8. The zirconium content in catalyst Cat-8 was 457 μmol / g catalyst.

[0121] Example 9

[0122] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0123] In a reactor, 2.0 g of dried porous POP-SNO-6 support containing [SO2NCO] groups was added, along with 1.0 mmol (0.377 g) of tetrachlorobistetrahydrofuranized zirconium ZrCl4(THF)2. The mixture was stirred at room temperature for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 0.5 hours. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-9. The zirconium content in catalyst Cat-9 was 356 μmol / g catalyst.

[0124] Example 10

[0125] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0126] (1) Preparation of 1-(vinylsulfonyl)-2-pyrrolidone [or N-(vinylsulfonyl)pyrrolidone] (L1-7) compounds:

[0127]

[0128] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of commercially available or synthetic vinylsulfonyl chloride (CAS: 6608-47-5), then 42 mmol of pyrrolidone (CAS: 616-45-5) and 45 mmol of triethylamine. The mixture was reacted at room temperature for 2 hours, filtered, and recrystallized from dichloromethane to prepare 1-(vinylsulfonyl)-2-pyrrolidone (L1-7) with a yield of 97%. Elemental Analysis: C, 41.1%; H, 5.2%; N, 8.0%; O, 27.4%; S, 18.3%.

[0129] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0130] In a reactor, 130 ml of isobutanol was added, followed by 5.0 g of divinylbenzene (55%) and 2.5 g of 1-(vinylsulfonyl)-2-pyrrolidone (L1-7). The mixture was stirred at room temperature for 5 min, and then 2% of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of AIBN was added. The temperature was raised to 70 °C and the reaction was carried out for 3 h at a speed of 450 rpm. The temperature was then raised to 80 °C and the reaction was carried out for 6 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 5.0 g of free-flowing porous organic polymer carrier POP-SNO-7 containing [SO2NCO] groups.

[0131] (3) Preparation of POP-SNO-Zr catalyst:

[0132] In a reactor, 2.0 g of dried porous POP-SNO-7 support containing [SO2NCO] groups was added, along with 1.28 mmol (approximately 0.3 g) of zirconium tetrachloride. The mixture was stirred at 10 °C for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 1 hour. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, denoted as Cat-10. The zirconium content in catalyst Cat-10 was 453 μmol / g catalyst.

[0133] Example 11

[0134] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0135] In a reactor, 2.0 g of dried porous POP-SNO-7 support containing [SO2NCO] groups was added, along with 1.2 mmol (approximately 0.45 g) of tetrachlorobistetrahydrofuranized zirconium ZrCl4(THF)2. The mixture was stirred at 10 °C for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 1 hour. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, designated Cat-11. The zirconium content in catalyst Cat-11 was 432 μmol / g catalyst.

[0136] Example 12

[0137] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0138] (1) Preparation of 5-methyl-1-(p-styrenesulfonyl)-2-pyrrolidone (L1-8) compound:

[0139]

[0140] In a reactor, 100 ml of dried dichloromethane was added, followed by 40 mmol of commercially available or synthetic p-styrenesulfonyl chloride (CAS: 2633-67-2), then 42 mmol of 5-methyl-2-pyrrolidone (CAS: 108-27-0) and 45 mmol of triethylamine. The reaction was carried out at room temperature for 2 hours. After filtration, the product was recrystallized from dichloromethane to prepare 5-methyl-1-(p-styrenesulfonyl)-2-pyrrolidone (L1-8) with a yield of 95%. Elemental analysis: C, 58.8%; H, 5.7%; N, 5.3%; O, 18.1%; S, 12.1%.

[0141] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0142] In a reactor, 130 ml of ethyl acetate was added, followed by 5.0 g of divinylbenzene (80%) and 3.0 g of 5-methyl-1-(p-styrenesulfonyl)-2-pyrrolidone (L1-8). The mixture was stirred at room temperature for 5 min, and then 2% (by mass) of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% (by mass) of AIBN was added. The temperature was raised to 70 °C, and the reaction was carried out for 3 h at a rotation speed of 450 rpm. The temperature was then raised to 80 °C, and the reaction was carried out for 6 h. After filtration, the mixture was washed three times with ethyl acetate, filtered, and dried to obtain 5.2 g of free-flowing porous organic polymer carrier POP-SNO-8 containing [SO2NCO] groups.

[0143] (3) Preparation of POP-SNO-Zr catalyst:

[0144] In a reactor, 2.0 g of dried porous POP-SNO-8 support containing [SO2NCO] groups was added, along with 1.0 mmol (approximately 0.24 g) of zirconium tetrachloride. The mixture was stirred at 10 °C for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 1 hour. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, designated Cat-12. The zirconium content in catalyst Cat-12 was 438 μmol / g catalyst.

[0145] Example 13

[0146] This embodiment provides an ethylene selective oligomerization catalyst, which is prepared by the following steps:

[0147] In a reactor, 2.0 g of dried porous POP-SNO-8 support containing [SO2NCO] groups was added, along with 1.0 mmol (approximately 0.377 g) of tetrachlorobistetrahydrofuranized zirconium ZrCl4(THF)2. The mixture was stirred at 10 °C for 3 hours, followed by the addition of 100 ml of dichloromethane and stirring for 1 hour. After filtration, the mixture was washed three times with hexane to obtain the POP-SNO-Zr main catalyst containing [SO2NCO] groups, designated Cat-13. The zirconium content in catalyst Cat-13 was 378 μmol / g catalyst.

[0148] Ethylene oligomerization was carried out using the catalysts in Examples 1-13.

[0149] Test Case 1-Test Case 13

[0150] In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 2ml of triethylaluminum (TEAL, 1.0 mol / L) were added as a purification agent. The stirring speed was 600 rpm. Then, 0.5g of the POP-supported Cat-1 to Cat-13 ethylene oligomerization catalyst prepared in Examples 1-13 were added, followed by a certain amount of diethylaluminum chloride (1.0 mol / L). The mixture was stirred for 3-5 minutes, heated to 70°C, and ethylene was introduced. The reaction was carried out at a pressure of 3.0 MPa and stirred at 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain the oligomer product. The composition of the oligomer product was determined by GC. 1 The α-olefin content in the oligomers was determined by HNMR, and the results are shown in Table 1.

[0151] Comparative Test Case 1

[0152] In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 2ml of triethylaluminum (TEAL, 1.0 mol / L) were added as a purification agent. The mixture was stirred at 600 rpm, followed by 0.1g of zirconium tetrachloride and then 10ml of diethylaluminum monochloro (1 mol / L). The mixture was stirred for 3-5 minutes, heated to 70°C, and ethylene was introduced. The reaction was carried out at a pressure of 3.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was complete, the mixture was cooled to obtain the product. The product composition was determined by GC. 1 The α-olefin content in the product was determined by HNMR, and the results are shown in Table 1.

[0153] Comparative Test Example 2

[0154] In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 2ml of triethylaluminum (TEAL, 1.0 mol / L) were added as impurity removers. The mixture was stirred at 600 rpm, followed by 0.1g of tetrachlorobis(tetrahydrofuran)zirconia ZrCl4(THF)2, and then 5ml of diethylaluminum chloride (1 mol / L). The mixture was stirred for 3-5 minutes, heated to 70°C, and ethylene was introduced. The reaction was carried out at a pressure of 3.0 MPa and stirred at 600 rpm for 1 hour. After the reaction was complete, the mixture was cooled to obtain the product. The product composition was determined by GC. 1 The α-olefin content in the product was determined by HNMR, and the results are shown in Table 1.

[0155] Comparative Test Case 3

[0156] In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 3ml of triethylaluminum (TEAL, 1.0 mol / L) were added as impurity removers. The mixture was stirred at 600 rpm, followed by the addition of 0.1g of [ZrCl4(Ph2SO2)]2 (using the [ZrCl4(Ph2SO2)]2 / AlEt2Cl disclosed in patent US20050070425A1), and then 5ml of diethylaluminum chloride (1 mol / L). The mixture was stirred for 3-5 minutes, heated to 70°C, and ethylene was introduced. The reaction was maintained at 3.0 MPa pressure and stirred at 600 rpm for 1 hour. After the reaction was complete, the mixture was cooled to obtain the product. The product composition was determined by GC. 1 The α-olefin content in the product was determined by HNMR, and the results are shown in Table 1.

[0157] Table 1 Results of ethylene oligomerization

[0158]

[0159] As shown in Table 1, the organic-supported ethylene oligomerization POP-SNO-Zr / organoaluminum catalyst system of this invention exhibits good ethylene oligomerization activity, reaching over 14000 g / gZr·h. The ethylene oligomerization products show good selectivity, with the total C4-C10 olefin content reaching over 90%, of which the C6-C10 olefin content is higher than 70%, reaching over 80%. The C6-C10 linear α-olefin selectivity is greater than 95%, reaching over 98% (C6-C10 linear α-olefin selectivity is the percentage of total C6-C10 linear α-olefins to total C6-C10).

Claims

1. An organic polymer carrier, which is obtained by copolymerization of monomers including divinylbenzene and functional monomers containing [SO2NCO] groups; in, The functional monomer containing the [SO2NCO] group has the structure shown in Formula I or Formula II: In Formula I, R1 is selected from single bonds, C1-C10 hydrocarbon groups and their derivatives; R2 and R3 may be the same or different, and are each independently selected from H, C1-C10 hydrocarbon groups and their derivatives. In Formula II, R1' is selected from single bonds, C1-C10 alkylene groups and their derivatives; R2' and R3' may be the same or different, and are each independently selected from C1-C10 alkylene groups and their derivatives.

2. The organic polymer carrier according to claim 1, wherein, In Formula I, R1 is selected from single bonds, methylene, ethylene, phenylene, and cycloalkylene; R2 and R3 may be the same or different, and are each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, chlorophenyl, and trifluoromethyl. In Formula II, R1' is selected from single bond, methylene, ethylene, phenylene, and cycloalkylene; R2' and R3' may be the same or different, and are each independently selected from methylene, ethylene, isopropylene, tert-butylene, phenylene, benzylene, chlorophenylene, and trifluoromethylene.

3. The organic polymer carrier according to claim 1, wherein, The functional monomer containing the [SO2NCO] group is selected from N-(vinylsulfonyl)-N-methylacetamide, N-(vinylsulfonyl)-N-ethylacetamide, N-(vinylsulfonyl)-N-tert-butylacetamide, N-(vinylsulfonyl)-N-phenylacetamide, N-(vinylsulfonyl)-N-phenylbenzamide, N-(vinylsulfonyl)-benzamide, N-(vinylsulfonyl)-phenylacetamide, N-(vinylsulfonyl)-N-benzylacetamide, N-(vinylsulfonyl)-N-benzylbenzamide, N-(vinylsulfonyl)-N-phenyl-2-chlorobenzamide, N-(vinylsulfonyl)-N-trifluoromethylphenylacetamide, N-(allylsulfonyl)-N-trifluoromethylphenylacetamide, N-(allylsulfonyl)-N-methylacetamide, N-(vin ... N-(allylsulfonyl)-formamide, N-(allylsulfonyl)-acetamide, N-(allylsulfonyl)-N-methylacetamide, N-(allylsulfonyl)-N-ethylacetamide, N-(allylsulfonyl)-N-tert-butylacetamide, N-(allylsulfonyl)-N-phenylformamide, N-(allylsulfonyl)-N-phenylacetamide, N-(allylsulfonyl)-N-phenylbenzamide, N-(allylsulfonyl)-benzamide, N-(allylsulfonyl)-N-phenylacetamide, N-(allylsulfonyl)-N-phenyl-2-chlorobenzamide, N-(allylsulfonyl)- N-Trifluoromethylphenylacetamide, N-(p-styrenesulfonyl)-formamide, N-(p-styrenesulfonyl)-acetamide, N-(p-styrenesulfonyl)-N-methylacetamide, N-(p-styrenesulfonyl)-N-ethylacetamide, N-(p-styrenesulfonyl)-N-tert-butylacetamide, N-(p-styrenesulfonyl)-N-phenylformamide, N-(p-styrenesulfonyl)-N-phenylacetamide, N-(p-styrenesulfonyl)-N-phenylbenzylacetamide, N-(p-styrenesulfonyl)-benzylacetamide, N-(p-styrenesulfonyl)-phenylacetamide, N-(p-styrenesulfonyl)-N-benzyl ... N-(1-)-N-benzylbenzamide, N-(p-styrenesulfonyl)-N-phenyl-2-chlorobenzamide, N-(p-styrenesulfonyl)-N-trifluoromethylphenylacetamide, N-(1-allylcyclopropanesulfonyl)-formamide, N-(1-allylcyclopropanesulfonyl)-acetamide, N-(1-allylcyclopropanesulfonyl)-N-methylacetamide, N-(1-allylcyclopropanesulfonyl)-N-ethylacetamide, N-(1-allylcyclopropanesulfonyl)-N-tert-butylacetamide, N-(1-allylcyclopropanesulfonyl)-N-phenylformamide, N-(1-allylcyclopropanesulfonyl)-N-phenylacetamide, N-(1-allylcyclopropanesulfonyl)-N-phenylbenzamide, N-(1-allylcyclopropanesulfonyl)-benzamide,N-(1-Allylcyclopropanesulfonyl)-phenylacetamide, N-(1-Allylcyclopropanesulfonyl)-N-benzylformamide, N-(1-Allylcyclopropanesulfonyl)-N-benzylacetamide, N-(1-Allylcyclopropanesulfonyl)-N-benzylbenzamide, N-(1-Allylcyclopropanesulfonyl)-N-phenyl-2-chlorobenzamide, N-(1-Allylcyclopropanesulfonyl)-N-trifluoromethylphenylacetamide, 1-(vinylsulfonyl)-2-pyrrolidone, 1-(enyl) One or more of the following: propylsulfonyl)-2-pyrrolidone, 1-(p-styrenesulfonyl)-2-pyrrolidone, 1-(1-allylcyclopropanesulfonyl)-2-pyrrolidone, 5-methyl-1-(vinylsulfonyl)-2-pyrrolidone, 5-methyl-1-(allylsulfonyl)-2-pyrrolidone, 5-methyl-1-(p-styrenesulfonyl)-2-pyrrolidone, and 5-methyl-1-(1-allylcyclopropanesulfonyl)-2-pyrrolidone.

4. The organic polymer carrier according to claim 1, wherein, Based on the mass of the organic polymer carrier being 100%, the mass fraction of the functional monomer containing the [SO2NCO] group is 10-70%.

5. A method for preparing the organic polymer carrier according to any one of claims 1-4, comprising the following steps: The organic polymer carrier is prepared by copolymerization using monomers including divinylbenzene and functional monomers containing [SO2NCO] groups as raw materials.

6. The preparation method according to claim 5, wherein, The organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization.

7. The preparation method according to claim 6, wherein, The dispersion polymerization method includes the following steps: Divinylbenzene and a functional monomer containing [SO2NCO] groups are added to a dispersion solvent, followed by the addition of a stabilizer and an initiator. The mixture is reacted at 50-80°C for 5-12 hours. After washing, filtration, and drying, the organic polymer carrier is obtained.

8. The preparation method according to claim 7, wherein, The reaction conditions for the dispersion polymerization method satisfy one or more of the following (1)-(8): (1) The dispersion solvent includes one or more of alcohols, fatty acid ester solvents, and tetrahydrofuran; (2) The total amount of monomer added is 1:5-20 in mass ratio to the dispersing solvent; (3) The mass ratio of the functional monomer containing the [SO2NCO] group to divinylbenzene is 0.2-2:1; (4) The stabilizer includes polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer; and / or, the weight average molecular weight of the stabilizer is 1,000-100,000; (5) The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-3:100; (6) The initiator includes azobisisobutyronitrile and / or benzoyl peroxide; (7) The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:100; (8) The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

9. The preparation method according to claim 5, wherein, The functional monomer containing the [SO2NCO] group is prepared by reacting a compound containing a sulfonyl chloride group with an amide compound under alkaline conditions; The amide compound has the general formula R2NHCOR3, where R2 and R3 may be the same or different, and are each independently selected from H, C1-C10 hydrocarbon groups and their derivatives; R2 and R3 may be linked together to form a ring; The general formula of the functional monomer containing sulfonyl chloride group is CH2=CH-R1-SO2Cl; R1 is selected from single bonds, C1-C10 alkylene groups and their derivatives.

10. An ethylene selective oligomerization catalyst, which is prepared by supporting a Zr compound on an organic polymer support as described in any one of claims 1-4.

11. The ethylene selective oligomerization catalyst according to claim 10, wherein, In the ethylene selective oligomerization catalyst, the Zr content is from 50 micromoles of Zr / gram catalyst to 800 micromoles of Zr / gram catalyst.

12. A method for preparing the ethylene selective oligomerization catalyst according to claim 10 or 11, comprising the following steps: The organic polymer support and zirconium compound precursor are reacted in equal amounts in an organic solvent at 0-40°C for 1-5 h to obtain the ethylene selective oligomerization catalyst.

13. The preparation method according to claim 12, wherein, The zirconium compound precursor includes one or more of zirconium tetrachloride, zirconium tetrachlorobistetrahydrofuranide, and chromium trihydrofuranide.

14. An ethylene selective oligomerization catalyst system, comprising the ethylene selective oligomerization catalyst of claim 10 or 11 and an organoaluminum co-catalyst.

15. The ethylene selective oligomerization catalyst system according to claim 14, wherein, The organoaluminum cocatalyst includes one or more of triethylaluminum, triisobutylaluminum, and diethylaluminum chloride.

16. The ethylene selective oligomerization catalyst system according to claim 14, wherein, In the ethylene selective oligomerization catalyst system, the molar ratio of Al to Zr is 1-500.

17. A method for preparing α-olefins by selective oligomerization of ethylene, comprising the following steps: using the selective oligomerization catalyst of claim 10 or 11, or the selective oligomerization catalyst system of any one of claims 14-16, to carry out the ethylene oligomerization reaction. In a reaction vessel, a solvent and a decontaminant are added, followed by the addition of the ethylene selective oligomerization catalyst and the organoaluminum co-catalyst. After mixing, the mixture is heated, and ethylene is introduced to carry out the reaction, thereby obtaining the ethylene oligomerization product.

18. The method according to claim 17, wherein, The content of C6-C10 olefin products in the ethylene oligomer is greater than 70%, and the selectivity of linear α-olefins in C6-C10 is greater than 95%.

19. The method of claim 17, wherein, The temperature of the ethylene oligomerization reaction is 20-80℃, and the partial pressure of ethylene is 1-10MPa.

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