Ethylene in-situ copolymerization catalyst system and application thereof

Abstract

The invention provides an ethylene in-situ copolymerization catalyst system and application thereof. The ethylene in-situ copolymerization catalyst system comprises an ethylene oligomerization catalyst, a metallocene copolymerization catalyst and an organic aluminum compound; the ethylene oligomerization catalyst is prepared by loading a Zr compound on an organic polymer carrier containing [SO2NCO] groups, the metallocene copolymerization catalyst is composed of an organic polymer carrier containing a [SO3] group, a metallocene compound and a cocatalyst. The ethylene in-situ copolymerization catalyst system can be polymerized to obtain linear low density polyethylene (LLDPE).

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to an in-situ copolymerization catalyst system for ethylene and its application. Background Technology

[0002] Polyethylene (PE) is the most commonly used polyolefin material, and linear low-density polyethylene (LLDPE), due to its high tear strength and impact resistance, has become the fastest-growing general-purpose plastic. LLDPE molecules have a linear structure with branches of a certain length, and its density is approximately 0.91-0.93 g·cm³. -3 LLDPE has superior performance compared to ordinary polyethylene, with significantly improved tear strength, puncture resistance, tensile strength and elongation at break. It is widely used in films, pipes, packaging and wires and cables.

[0003] LLDPE is generally prepared by first oligomerizing ethylene to obtain α-olefins, which are then separated, purified, and copolymerized with ethylene again—a two-step process. Beach and Kissin proposed a bifunctional catalytic system for the in-situ copolymerization of ethylene to LLDPE. This involves adding both the oligomerization and copolymerization catalysts to the same polymerization apparatus. Ethylene first produces α-olefins on the oligomerization catalyst, which are then immediately reacted with excess ethylene through the copolymerization catalyst to produce LLDPE. Compared to the stepwise process, the most significant advantage of this one-pot method is that it uses only ethylene as the monomer feedstock. The α-olefin comonomer is obtained from the oligomerization catalyst within the system, eliminating the steps of α-olefin synthesis, purification, and storage. This simplifies the production process and significantly reduces production costs, thus attracting considerable attention. Beach and Kissin used the Ziegler-Natta catalytic system and nickel-based catalysts as oligomerization catalysts for the in-situ preparation of LLDPE. However, as the amount of oligomerization catalyst increases, the polymerization activity decreases. Since methylaluminoxane (MAO) is usually added to the catalyst, interference exists between catalysts, resulting in incomplete catalyst system matching and unstable product structure. When metallocene oxide (MAO) is selected as a cocatalyst, it exhibits high activity and selectivity, and the resulting polymers have a narrow molecular weight distribution. These significant advantages have made it a focus of attention in the field of olefin polymerization catalysts. Therefore, metallocene catalysts are currently mainly used as copolymerization catalysts in bifunctional catalyst systems for the in-situ copolymerization of ethylene to prepare linear low-density polyethylene.

[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 / g Zr.h. The linear α-olefin content of C4-C8 components can reach over 85%, of which the C6-C8 content can reach over 50%.

[0006] CN102336855A discloses an in-situ copolymerization catalytic system for ethylene. The catalyst comprises an oligomerization catalyst supported on an inorganic support of MgCl2 / SiO2, a copolymerization catalyst supported on MgCl2 / SiO2, and an alkylaluminoxane. The oligomerization catalyst is an α-diimine pyridine iron complex, and the copolymerization catalyst is a metallocene complex with Zr as the central atom. The catalyst system is suitable for in-situ polymerization of ethylene at 50-90℃ in gas-phase and slurry polymerization, exhibiting high catalyst activity, high bulk density of the obtained polymer, and low fine powder content. However, the ethylene oligomerization catalyst has low selectivity for α-C4-C8 olefins, and the branched structure of the polymer is relatively complex. Frediani et al. (Frediani M., Bianchini C. et al., Low density polyethylene by tandem catalysis with single-site Ti(IV) / Co(II) catalysts. Kinet Catal., 2006, Vol. 47, No. 2, pp. 207-212.) used a cobalt pyridinium imide oligomerization catalyst and CGC-Ti as an in-situ copolymerization catalyst system, with MAO as a co-catalyst. Polymerization was carried out at 30°C and 3 atm ethylene pressure. The oligomerization catalyst showed a selectivity of over 80% for 1-butene, with a maximum catalytic activity of up to 10. 6 g·mol -1 ·h -1Increased steric hindrance of substituents on the pyridine ring leads to increased molecular weight distribution and branching of the polymer. However, this catalyst system employs homogeneous polymerization, making polymer separation and processing complex. BIANCHINI et al. (BIANCHINI C, GIAMBASTIANI G et al., LLDPE with Exclusively Ethyl Branches by Tandem Catalysis with Single-Site Zr(IV) / Co(II) Catalysts. Top Catalysts, 2008, Vol. 48 (1 / 4): 107-113.) used the classic copolymerization catalyst Cp2ZrCl2 and cobalt pyridineimine catalyst to form bifunctional catalyst systems. These systems exhibited high activity in in-situ copolymerization of ethylene under the action of the co-catalyst MAO. KUWABARA et al. (KUWABARA J, TAKEUCHID et al., Early-late heterobimetallic complexes as initiator for ethylene polymerization. Cooperative effect of two metal centers to afford highly branched polyethylene. Chem Commun, 2006, Vol. 36, pp. 3815-3817.) constructed a heterobinuclear complex by chemically bonding a pre-transition metal zirconium with copolymerizing properties and a non-ceramic post-transition metal with oligomeric properties into a single complex. This complex possessed both oligomeric and copolymerizing active centers, and under the action of the co-catalyst MMAO, successfully catalyzed the in-situ polymerization of ethylene to obtain long-chain branched polyethylene containing ethyl groups and more than C6 atoms. Compared with the corresponding mixed catalytic system composed of two independent mononuclear complexes, the resulting polymer had a higher degree of branching and a narrower molecular weight distribution. Summary of the Invention

[0007] To address the aforementioned problems, the present invention aims to provide an ethylene in-situ copolymerization catalyst system and its application. This ethylene in-situ copolymerization catalyst system can polymerize linear low-density polyethylene (LLDPE).

[0008] To achieve the above objectives, the present invention provides an ethylene in-situ copolymerization catalyst system, comprising an ethylene oligomerization catalyst, a metallocene copolymerization catalyst, and an organoaluminum compound; the ethylene oligomerization catalyst is prepared by loading a Zr compound onto an organic polymer support containing [SO2NCO] groups; the organic polymer support containing [SO2NCO] groups is prepared by copolymerization of a monomer comprising divinylbenzene and a functional monomer containing [SO2NCO] groups (denoted as monomer L1); wherein the functional monomer containing [SO2NCO] groups has the structure shown in Formula I or Formula II:

[0009]

[0010] 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.

[0011] 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.

[0012] The metallocene copolymer catalyst is composed of an organic polymer support containing [SO3] groups, a metallocene compound, and a co-catalyst; the organic polymer support containing [SO3] groups is a copolymer of divinylbenzene and functional monomers containing [SO3] groups by acidification, and the functional monomers containing [SO3] groups include styrene containing sulfonic acid groups and / or olefins containing sulfonic acid groups.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] According to a specific embodiment of the present invention, preferably, the functional monomer containing the [SO3] group includes sodium p-styrene sulfonate, p-styrene sulfonic acid, sodium m-styrene sulfonate, m-styrene sulfonic acid, o-styrene sulfonic acid, sodium o-styrene sulfonate, sodium 2-methyl-4-sulfonate styrene, 2-methyl-4-sulfonate styrene, sodium 2-methyl-3-sulfonate styrene, 2-methyl-3-sulfonate styrene, vinyl-4-methylbenzene sulfonic acid, sodium vinyl-4-methylbenzene sulfonate, sodium 2-ethyl-3-sulfonate styrene, 2-ethyl-3-sulfonate styrene, 4,4'-bis(2-sulfonate styrene)-1, 1'-Biphenyl, 2-(2-styryl)benzenesulfonic acid, vinyl sulfonic acid, sodium vinyl sulfonate, propylene sulfonic acid, sodium propylene sulfonate, methpropylene sulfonic acid, sodium methpropylene sulfonate, 1-butenyl sulfonic acid, sodium 1-butenyl sulfonate, 1-pentenyl sulfonic acid, sodium 1-pentenyl sulfonate, 1-hexene sulfonic acid, sodium 1-hexene sulfonate, 1-heptene sulfonic acid, sodium 1-heptene sulfonate, 1-octenyl sulfonic acid, sodium 1-octenyl sulfonate, methacrylic acid-2-ethanesulfonic acid, sodium methacrylic acid-2-ethanesulfonic acid, 2-acrylamido-2-methyl-1-propane sulfonic acid, sodium allyl sulfonate, and one or more combinations of their hydrates.

[0017] According to a specific embodiment of the present invention, preferably, based on the mass of the organic polymer carrier containing the [SO2NCO] group as 100%, the mass fraction of the functional monomer containing the [SO2NCO] group is 10%-70%, more preferably 20-60%.

[0018] According to a specific embodiment of the present invention, preferably, based on the mass of the organic polymer carrier containing the [SO3] group as 100%, the mass fraction of the functional monomer containing the [SO3] group is 5%-60%, more preferably 20-50%.

[0019] According to a specific embodiment of the present invention, preferably, the metallocene compound has the general formula Cp. x MA y B z In this general formula, Cp is selected from unsubstituted cyclopentadienyl, substituted cyclopentadienyl, indenyl, fluorenyl, indenyl ligand in hydrogenated form, or fluorenyl ligand in hydrogenated form; M is a group IVB transition metal element (preferably zirconium or hafnium); A and B are each independently selected from halogen atoms, hydrogen atoms, or alkyl groups (preferably chlorine atoms); x is an integer from 1 to 3 (preferably 2); and y and z are integers from 0 to 3. When x equals 2 in the general formula, the Cp ligand can also be bridged by polymethylene or dialkylsilane, such as -Si(CH3)2-, -C(CH3)2-, -CH2-, -CH2-CH2-, etc.; more preferably, y+z≤3, x+y+z=4; more preferably, when A and B are alkyl groups, the alkyl group is selected from C1-C8 straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, or n-pentyl.

[0020] According to a specific embodiment of the present invention, preferably, the co-catalyst is an alkylaluminoxane compound.

[0021] According to a specific embodiment of the present invention, preferably, the metallocene compound includes one or more combinations of bis(cyclopentadienyl) metal dihalides, bis(cyclopentadienyl) metal monoalkyl monohalides, bis(cyclopentadienyl) metal dialkyl compounds, and bis(indenyl) metal dihalides, more preferably bis(cyclopentadienyl) metal dialkyl compounds and / or bis(indenyl) metal dihalides, wherein the halogen group is more preferably chlorine, and the alkyl group is more preferably C1-C6 alkyl.

[0022] According to a specific embodiment of the present invention, preferably, the metallocene compound is selected from di(cyclopentadienyl)zirconia, di(cyclopentadienyl)dimethylzirconia, di(n-butylcyclopentadienyl)zirconia, di(n-butylcyclopentadienyl)dimethylzirconia, di(dimethylcyclopentadienyl)dimethylzirconia, diindylzirconia, methylene-bridged diindylzirconia, di(4,5,6,7-tetrahydro-1-indyl)zirconia, ethylidene-bridged di(indyl)zirconia, dimethylsilyl-bridged bis(2-methyl)zirconia. (-4-phenylindenyl)zirconia dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)dimethylzirconia, dimethylsilyl-bridged bis(2-methylindenyl)zirconia dichloride, dimethylsilyl-bridged bis(2-methyl-benzoindenyl)zirconia dichloride, dimethylsilyl-bridged bis(2-methyl-benzoindenyl)dimethylzirconia, dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)dimethylzirconia, methylsilyl-bridged bis(2-methyl-4-phenylindenyl)dimethylzirconia, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)dimethyl Hafnium dichloride, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)dimethylhafnium, bis(dimethylcyclopentadienyl)dimethylhafnium, diindylhafnium dichloride, methylene-bridged diindylhafnium dichloride, bis(4,5,6,7-tetrahydro-1-indyl)hafnium dichloride, ethylidene-bridged bis(indyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)dimethylhafnium, dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)dimethylhafnium, dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)dimethylhafnium The following are one or more combinations of hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-benzo[indene]) hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-benzo[indene]) dimethyl hafnium, dimethylsilyl-bridged bis(2-methyl-indene) dimethyl hafnium, methylsilyl-bridged bis(2-methyl-4-phenylindene) dimethyl hafnium, ethylidene-bridged bis(indene) zirconium dichloride, ethylidene-bridged bis(indene) hafnium dichloride, bis(n-butylcyclopentadienyl) zirconium dichloride, and bis(1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride.

[0023] According to a specific embodiment of the present invention, preferably, the co-catalyst comprises methylaluminoxane (MAO), and when methylaluminoxane (MAO) is selected as the co-catalyst, the resulting metallocene copolymerization catalyst is denoted as POP-SO3-MAO / M.

[0024] According to a specific embodiment of the present invention, preferably, the Zr content in the ethylene 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.

[0025] According to a specific embodiment of the present invention, preferably, in the metallocene copolymer catalyst, the co-catalyst is calculated as Al, the metallocene compound is calculated as M, and the molar ratio of co-catalyst to metallocene compound Al:M is 50-500, more preferably 75-200; the co-catalyst, calculated as Al, has a content of 1 mmol / g catalyst to 12 mmol / g catalyst, more preferably 4 mmol / g catalyst to 8 mmol / g catalyst; the content of metal atoms M, the metal active center of the metallocene compound, is 5 μmol / g catalyst to 100 μmol / g catalyst, more preferably 10-100 μmol / g catalyst, more preferably 20-50 μmol / g catalyst.

[0026] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes one or more of triethylaluminum, triisobutylaluminum, and diethylaluminum chloride, more preferably diethylaluminum chloride; when diethylaluminum chloride is selected as the organoaluminum compound, it forms an ethylene oligomerization catalyst system with the ethylene oligomerization catalyst, denoted as POP-SNO-Zr / AlEt2Cl.

[0027] According to a specific embodiment of the present invention, preferably, the molar ratio of Al in the organoaluminum compound to Zr in the ethylene oligomerization catalyst is 1-500, more preferably 5-200.

[0028] According to a specific embodiment of the present invention, preferably, the molar ratio of Zr in the ethylene oligomerization catalyst to M in the metallocene copolymerization catalyst is 50:1-1:10, more preferably 10:1-1:1.

[0029] According to a specific embodiment of the present invention, preferably, the method for preparing the organic polymer carrier containing [SO2NCO] groups includes the following steps: using monomers comprising divinylbenzene and functional monomers containing [SO2NCO] groups as raw materials, the organic polymer carrier containing [SO2NCO] groups (denoted as POP-SNO) is obtained by copolymerization, wherein the content of functional monomers containing [SO2NCO] groups in POP-SNO is determined by the amount of divinylbenzene and functional monomer L1 containing [SO2NCO] groups added; the structure of the organic polymer carrier containing [SO2NCO] groups is shown in Formula III or Formula IV:

[0030]

[0031] 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;

[0032] 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.

[0033] According to a specific embodiment of the present invention, preferably, the preparation method of the ethylene oligomerization catalyst includes the following steps:

[0034] (1) Preparation of organic polymer carriers containing [SO2NCO] groups: The carriers are prepared by free radical polymerization, such as dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization. The dispersion polymerization method is as follows: divinylbenzene and functional monomers containing [SO2NCO] groups are added to a dispersion solvent, then a stabilizer and an initiator are added, and the reaction is carried out at 50-80℃ for 5-12 hours. After washing, filtration and drying, the organic polymer carriers containing [SO2NCO] groups are obtained.

[0035] (2) Zr compound loading: Zr compound is loaded onto the organic polymer support containing [SO2NCO] groups obtained in step (1) using zirconium compound precursor to obtain the ethylene oligomerization catalyst, denoted as POP-SNO-Zr.

[0036] The metallocene copolymer catalyst of the present invention can be prepared according to CN115073627B and CN115073628B. According to a specific embodiment of the present invention, preferably, the preparation method of the metallocene copolymer catalyst includes the following steps:

[0037] (a) Add divinylbenzene and the functional monomer containing the [SO3] group to a dispersion solvent consisting of a C1-C4 alcohol or a mixture of C1-C4 alcohol and water, dissolve the stabilizer in the system at 20-50°C, then add the initiator, heat to 60-80°C, react for 3-12 hours, and wash away impurities after the reaction is complete.

[0038] (b) Add dilute acid and carry out an acidification reaction at 20-70℃. Wash and dry to obtain the organic polymer carrier containing [SO3] groups.

[0039] (c) The organic polymer support containing [SO3] groups obtained in step (b) is added to an inert solvent under anhydrous and oxygen-free operating conditions, then a co-catalyst is added, and the reaction is carried out for 15-120 minutes. Then, a metallocene compound is added, the temperature is adjusted to -20°C to 40°C, and the reaction is carried out for 15-180 minutes. After washing with an inert solvent, the metallocene copolymer catalyst is obtained. The co-catalyst used needs to be supported on the organic polymer support containing [SO3] groups. Then, the metallocene compound is supported on the organic polymer support containing [SO3] groups after co-catalyst treatment to obtain the metallocene catalyst supported on the organic polymer support containing [SO3] groups.

[0040] According to a specific embodiment of the present invention, preferably, in the method for preparing the ethylene oligomerization catalyst, the reaction conditions of the dispersion polymerization method satisfy one or more of the following conditions (1)-condition (8), and step (2) satisfies the following conditions (10) and / or condition (11); the reaction conditions of the method for preparing the metallocene copolymerization catalyst satisfy one or more of the following conditions (1)-condition (9):

[0041] Condition (1): The dispersing solvent in step (1) includes one or more of alcohols, fatty acid ester solvents, and tetrahydrofuran; or, in the dispersing solvent of step (a), the C1-C4 alcohol includes one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol, and the mass ratio of C1-C4 alcohol to water in the C1-C4 alcohol-water mixture is 5-15:1;

[0042] Condition (2): The mass ratio of the total amount of monomer added to the mass of the dispersing solvent is 1:5-20;

[0043] Condition (3): The mass ratio of the functional monomer containing the [SO2NCO] group or the functional monomer containing the [SO3] group to the mass of divinylbenzene is 0.2-2:1;

[0044] Condition (4): The stabilizer comprises polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer;

[0045] Condition (5): The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-3:100;

[0046] Condition (6): The initiator comprises azobisisobutyronitrile and / or benzoyl peroxide;

[0047] Condition (7): The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:100;

[0048] Condition (8): The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor;

[0049] Condition (9): The dilute acid is dilute hydrochloric acid or dilute sulfuric acid;

[0050] Condition (10): Step (2) of the preparation method of the ethylene oligomerization catalyst is to react the organic polymer support containing [SO2NCO] groups and the zirconium compound precursor in equal amounts in an organic solvent (e.g., dichloromethane) at 0-40°C for 1-5 h to obtain the ethylene selective oligomerization catalyst.

[0051] Condition (11): The zirconium compound precursor includes one or more of zirconium tetrachloride, zirconium tetrachlorobistetrahydrofuranide, and chromium trihydrofuranide.

[0052] According to a specific embodiment of the present invention, preferably, the preparation method of the organic polymer carrier containing [SO3] groups includes the following steps: adding divinylbenzene and a functional monomer containing [SO3] groups (such as sodium p-styrene sulfonate, vinyl sulfonic acid) to a dispersion solvent; styrene is optional. Then, a stabilizer and an initiator are added, and after stirring and dispersing evenly, the mixture is reacted at 50-80°C for 5-12 hours. After filtration, acidification with dilute sulfuric acid is performed, followed by washing, filtration, and drying to obtain the porous organic polymer carrier.

[0053] According to a specific embodiment of the present invention, preferably, the preparation method of the metallocene copolymer catalyst includes the following steps: first, the above-mentioned organic polymer support containing [SO3] groups is vacuum dried to remove residual water and air from the support; under anhydrous and oxygen-free operating conditions, the above-mentioned organic polymer support containing [SO3] groups is added to an inert solvent, then MAO co-catalyst is added, and the mixture is stirred at room temperature for 15-120 minutes; then the metallocene compound Cp... x MA y B z The compound was added to the reaction solution, the temperature was adjusted to 0℃-40℃, and the reaction was carried out for 15-180 minutes. After washing with an inert solvent such as toluene or hexane, the metallocene copolymer catalyst was obtained.

[0054] According to a specific embodiment of the present invention, preferably, the dispersing solvent in step (1) contains alcohols including, but not limited to, one or more combinations of ethanol, propanol, isopropanol, and isobutanol.

[0055] According to a specific embodiment of the present invention, preferably, the dispersing solvent in step (1) 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.

[0056] According to a specific embodiment of the present invention, preferably, the weight-average molecular weight of the stabilizer used in the preparation method of the ethylene oligomerization catalyst is 1000-100000.

[0057] According to a specific embodiment of the present invention, preferably, the weight-average molecular weight of the stabilizer used in the preparation method of the metallocene copolymer catalyst is 6,000-100,000.

[0058] 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, where 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; R2 and R3 can be bonded together 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 alkylene groups and their derivatives, such as methylene, ethylene, phenylene, and when R1 is a single bond, it indicates that the carbon atom connected to R1 is directly bonded to the S atom, and the structure of L2 is shown in Formula V;

[0059]

[0060] 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%.

[0061] 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.

[0062] 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).

[0063] The present invention also provides the application of the above-mentioned ethylene in-situ copolymerization catalyst system in ethylene polymerization, which includes the following steps: adding solvent, the ethylene oligomerization catalyst, the metallocene copolymerization catalyst, and the organoaluminum compound to a reaction vessel, introducing ethylene, and heating to react to obtain an ethylene in-situ copolymer.

[0064] According to a specific embodiment of the present invention, preferably, the temperature of the ethylene polymerization is 50-80°C and the pressure is 0.1-3.0 MPa.

[0065] According to a specific embodiment of the present invention, preferably, the polyethylene obtained by ethylene polymerization has a density of 0.88-0.94 g / ml.

[0066] According to a specific embodiment of the present invention, preferably, the ethylene polymerization is a gas-phase polymerization reaction or a slurry polymerization reaction; the solvent used in the slurry polymerization reaction is a C5-C10 alkane, more preferably hexane.

[0067] In this invention, the ethylene in-situ copolymerization catalyst system is composed of an ethylene oligomerization catalyst system and a metallocene copolymerization catalyst. (1) In the ethylene oligomerization catalyst system, a porous POP support (POP-SNO) containing [SO2NCO] groups is obtained by copolymerizing divinylbenzene with functional monomers containing [SO2NCO] groups. Based on the [SO2NCO] ligands on the POP-SNO support, the zirconium metal active center is fixed on the POP-SNO support. When used for polymerization, it reacts with co-catalysts such as organoaluminum compounds (e.g., diethylaluminum chloride) to obtain an organically supported “POP-SNO-Zr / organoaluminum” ethylene oligomerization catalyst system; (2) In the organically supported ethylene copolymerization catalyst, a porous POP support containing [SO3] groups is obtained by copolymerizing divinylbenzene with functional monomers containing [SO3] groups. After acidification, a POP support containing [SO3H] groups is obtained. After contacting with MAO co-catalyst and metallocene compound respectively, a POP-SO3-MAO / M (M is preferably Zr or Hf) ethylene copolymerization catalyst is obtained.

[0068] The above-mentioned ethylene oligomerization catalyst system is suitable for the preparation of α-olefins, especially 1-C6 and 1-C8 linear α-olefins, by ethylene oligomerization. The suitable reaction conditions for ethylene oligomerization are a temperature of 20-80℃ and an ethylene partial pressure of 1-10 MPa. The solvent for slurry polymerization can be selected from C5-C10 alkanes, such as one or more combinations of hexane, cyclohexane, toluene, and methylcyclohexane, preferably methylcyclohexane. A small amount of alkyl aluminum, such as triethylaluminum, can be added during polymerization to remove trace amounts of water from the solvent. The ethylene oligomerization catalyst system supported on an organic polymer support disclosed in this invention mainly yields C4-C10 linear α-olefins in ethylene oligomerization, exhibiting good catalytic activity and selectivity for C4-C10 linear α-olefins, with high content and purity of C6-C10 olefins. The metallocene copolymerization catalyst supported on the organic support also exhibits good copolymerization performance.

[0069] The ethylene oligomerization catalyst system (i.e., composed of the ethylene oligomerization catalyst and organoaluminum compounds) and the POP-SO3-MAO / M metallocene copolymerization catalyst constitute an in-situ copolymerization catalyst system. Using a single ethylene feedstock, ethylene oligomers can be copolymerized with ethylene to prepare highly branched LLDPE products.

[0070] The present invention has the following beneficial effects:

[0071] 1. The ethylene oligomerization catalyst system used in the ethylene in-situ copolymerization catalyst system has good catalytic activity and short-chain olefin selectivity. The polymerization of the ethylene in-situ copolymerization catalyst system can obtain linear low-density polyethylene (LLDPE), whose molecular chain mainly consists of short branches containing 2-8 carbon atoms.

[0072] 2. LLDPE can be directly prepared using an in-situ copolymerization catalyst system of ethylene, exhibiting good polymerization activity and producing polymers with good morphology and no agglomeration. The density of polyethylene can be controlled between 0.88-0.94 g / ml.

[0073] 3. By adjusting the ratio of ethylene oligomerization catalyst to metallocene copolymerization catalyst, the phenomenon of sticking to the reactor can be avoided during the polymerization process, and the polymer can be obtained through simple separation and drying processes. Detailed Implementation

[0074] 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.

[0075] Raw material source:

[0076] The monomer divinylbenzene (DVB) used below can be a commercially available monomer with a DVB content of 55% or 80%. Divinylbenzene requires pretreatment before use to remove polymerization inhibitors. Methods for removing polymerization inhibitors can follow existing techniques; for example, divinylbenzene can be washed with sodium hydroxide solution and distilled water, then dried with anhydrous magnesium sulfate before use. Styrene should be treated with a 10% NaOH solution to remove polymerization inhibitors before use, followed by washing three times with deionized water.

[0077] Evaluation and analysis methods: The composition of the oligomers was determined by gas chromatography (GC). 1 The specific content of the components was determined by HNMR. The melting point was determined using a DSC Q2000 differential scanning calorimeter. Elemental analysis (PerkinElmer 2400II) was used to verify the synthesis of the monomers.

[0078] Example 1

[0079] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0080] (1) Preparation of N-(vinylsulfonyl)-N-methylacetamide (L1-1) functional monomer:

[0081]

[0082] In a reaction flask, 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%.

[0083] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0084] 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% 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 4.7 g of free-flowing porous organic polymer carrier POP-SNO-1 containing [SO2NCO] groups.

[0085] (3) Preparation of POP-SNO-Zr catalyst:

[0086] 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 catalyst containing [SO2NCO] groups, denoted as Cat-1. The zirconium content in catalyst Cat-1 was 387 μmol / g catalyst.

[0087] Example 2

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

[0089] (1) Preparation of N-(vinylsulfonyl)-N-methylbenzamide (L1-2) functional monomer:

[0090]

[0091] In a reaction flask, 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. After filtration, N-(vinylsulfonyl)-N-methylbenzamide (L1-2) was prepared by recrystallization with dichloromethane, yielding 95%. Elemental Analysis: C, 53.3%; H, 4.9%; N, 6.2%; O, 21.4%; S, 14.2%.

[0092] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0093] 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.

[0094] (3) Preparation of POP-SNO-Zr catalyst:

[0095] 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 catalyst containing [SO2NCO] groups, denoted as Cat-2. The zirconium content in catalyst Cat-2 was 415 μmol / g catalyst.

[0096] Example 3

[0097] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0098] (1) Preparation of N-(allylsulfonyl)-N-methylbenzamide (L1-3) functional monomer:

[0099]

[0100] 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."

[0101] In a reaction flask, 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%.

[0102] In a reaction flask, 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), yield 96%; Elemental Analysis: C, 55.2%; H, 5.5%; N, 5.8%; O, 20.1%; S, 13.4%.

[0103] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0104] 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.

[0105] (3) Preparation of POP-SNO-Zr catalyst:

[0106] 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 catalyst containing [SO2NCO] groups, denoted as Cat-3. The zirconium content in catalyst Cat-3 was 423 μmol / g catalyst.

[0107] Example 4

[0108] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0109] (1) Preparation of N-(p-styrenesulfonyl)-N-methylbenzamide (L1-4) functional monomer:

[0110]

[0111] In a reaction flask, 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%.

[0112] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0113] 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.

[0114] (3) Preparation of POP-SNO-Zr catalyst:

[0115] 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 catalyst containing [SO2NCO] groups, denoted as Cat-4. The zirconium content in catalyst Cat-4 was 392 μmol / g catalyst.

[0116] Example 5

[0117] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0118] 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 catalyst containing [SO2NCO] groups, designated Cat-5. The zirconium content in catalyst Cat-5 was 354 μmol / g catalyst.

[0119] Example 6

[0120] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0121] (1) Preparation of N-(p-styrenesulfonyl)-N-phenyl-2-chlorobenzamide (L1-5):

[0122]

[0123] In a reaction flask, 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%.

[0124] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0125] 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.

[0126] (3) Preparation of POP-SNO-Zr catalyst:

[0127] 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 catalyst containing [SO2NCO] groups, designated Cat-6. The zirconium content in catalyst Cat-6 was 375 μmol / g catalyst.

[0128] Example 7

[0129] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0130] 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 catalyst containing [SO2NCO] groups, designated Cat-7. The zirconium content in catalyst Cat-7 was 318 μmol / g catalyst.

[0131] Example 8

[0132] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0133] (1) Preparation of N-(1-allylcyclopropanesulfonyl)-N-ethylacetamide:

[0134]

[0135] In a reaction flask, 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. After filtration, the product was 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%.

[0136] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0137] 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.

[0138] (3) Preparation of POP-SNO-Zr catalyst:

[0139] 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 catalyst containing [SO2NCO] groups, designated Cat-8. The zirconium content in catalyst Cat-8 was 457 μmol / g catalyst.

[0140] Example 9

[0141] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0142] 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 catalyst containing [SO2NCO] groups, designated Cat-9. The zirconium content in catalyst Cat-9 was 356 μmol / g catalyst.

[0143] Example 10

[0144] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0145] (1) Preparation of 1-(vinylsulfonyl)-2-pyrrolidone [or N-(vinylsulfonyl)pyrrolidone] (L1-7) compounds:

[0146]

[0147] In a reaction flask, 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 reaction was carried out 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%.

[0148] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0149] 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 4.7 g of free-flowing porous organic polymer carrier POP-SNO-7 containing [SO2NCO] groups.

[0150] (3) Preparation of POP-SNO-Zr catalyst:

[0151] 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 catalyst containing [SO2NCO] groups, designated Cat-10. The zirconium content in catalyst Cat-10 was 453 μmol / g catalyst.

[0152] Example 11

[0153] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0154] (1) Preparation of 5-methyl-1-(p-styrenesulfonyl)-2-pyrrolidone (L1-8) compound:

[0155]

[0156] In a reaction flask, 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 mixture 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%.

[0157] (2) Preparation of porous organic polymer supports containing [SO2NCO] groups:

[0158] 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, followed by 2.0% (by mass) of AIBN. 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.

[0159] (3) Preparation of POP-SNO-Zr catalyst:

[0160] 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 catalyst containing [SO2NCO] groups, designated Cat-11. The zirconium content in catalyst Cat-11 was 438 μmol / g catalyst.

[0161] Ethylene oligomerization was carried out using catalysts Cat-1 to Cat-11 from Examples 1-11.

[0162] Test Case 1-Test Case 11

[0163] 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-11 ethylene oligomerization catalyst prepared in Examples 1-11 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.

[0164] Table 1 Results of ethylene oligomerization

[0165]

[0166]

[0167] As shown in Table 1, the ethylene oligomerization catalyst system supported on the organic support in this invention has good ethylene oligomerization activity, which can reach more than 14000 g / g Zr.h. The ethylene oligomerization products have good selectivity, with a total C4-C10 olefin content of more than 90%, and a C4-C10 olefin content of more than 98%. Among them, the C6-C10 olefin content is higher than 70%, reaching more than 80%. The linear α-olefin selectivity among C6-C10 olefins is higher than 95%, reaching more than 98% (the C6-C10 linear α-olefin selectivity is the percentage of the total C6-C10 linear α-olefins to the total C6-C10).

[0168] Example 12

[0169] This embodiment provides a metallocene copolymerization catalyst, which is prepared by the following steps:

[0170] (1) Preparation of porous organic polymer carriers:

[0171] In the reactor, add 120 ml of ethanol and 10 ml of deionized water, then add 5.0 g of 80% divinylbenzene and 2.0 g of sodium p-styrene sulfonate. Stir at room temperature for 5 minutes, then add 2% (by weight of total monomers) of polyvinyl alcohol (trade name: [product name missing]). Polyvinyl alcohol stabilizer was dissolved and AIBN (2% of the total monomer mass) was added at 45°C for 1 hour. The temperature was raised to 70°C and reacted for 3 hours. Then the temperature was raised to 80°C and reacted for 5 hours. The stirring speed was 450 rpm. The mixture was washed 3 times with ethanol / water (volume ratio: 1:1). It was then reacted 0.5 hours at 50°C with 10 ml of 10% dilute sulfuric acid. This treatment was repeated twice. The mixture was washed 3 times with the above ethanol / water mixture. After filtration and drying, a porous organic polymer carrier POP-SO3H-1 was obtained.

[0172] (2) Preparation of metallocene copolymerization catalysts:

[0173] 4.5 g of porous organic polymer support POP-SO3H-1 was vacuum filtered at 120 °C for 8 hours using a vacuum dryer. The treated POP-SO3H-1 support was added to a 250 ml nitrogen-purged reactor, along with 100 ml of dried toluene and 2.5 g of white MAO granules. The mixture was stirred at 45 °C for 1 hour. Then, 0.18 g of En(Ind)2ZrCl2 (ethylene-bridged bis-indene dizirconia) metallocene compound and 10 ml of toluene were added, and the mixture was stirred for 0.5 hours. The reaction was then carried out at 25 °C for 3 hours. After the reaction, the solvent was removed, and the mixture was dried to obtain the POP-SO3-MAO / Zr metallocene copolymer catalyst, denoted as Cat-M1. Catalyst Cat-M1 contained 38.7 μmol / g of Zr and 6.5 mmol / g of aluminum.

[0174] Example 13

[0175] This embodiment provides a metallocene copolymerization catalyst, which is prepared by the following steps:

[0176] 4.5 g of porous organic polymer support POP-SO3H-1 was vacuum filtered at 120 °C for 8 hours using a vacuum dryer. The treated support POP-SO3H-1 was added to a 250 ml nitrogen-purged reactor, along with 100 ml of dried toluene and 2.5 g of white MAO granules. The mixture was stirred at 25 °C for 1 hour, followed by 0.16 g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienylzirconium dichloride) metallocene compound and 10 ml of toluene. The mixture was stirred for 0.5 hours and then reacted at 25 °C for 3 hours. After the reaction, the solvent was removed, and the mixture was dried to obtain the POP-SO3-MAO / Zr metallocene copolymer catalyst, denoted as Cat-M2. The catalyst Cat-M2 contained 31.5 μmol / g of Zr and 6.3 mmol / g of aluminum.

[0177] Example 14

[0178] This embodiment provides a metallocene copolymerization catalyst, which is prepared by the following steps:

[0179] (1) Preparation of porous organic polymer carriers:

[0180] In a reactor, 110 ml of ethanol and 12 ml of deionized water were added, followed by 2 ml of styrene, 6.0 g of 80% divinylbenzene, and 3.0 g of sodium allyl sulfonate. The mixture was stirred at room temperature for 5 min, and then 2% of the total monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 0.5 h, and then 2% of the total monomer mass of AIBN was added. The temperature was raised to 70 °C and reacted for 3 h. The temperature was then raised to 80 °C and reacted for 5 h. The stirring speed was 450 rpm. The mixture was washed three times with ethanol / water (volume ratio: 1:1), and then reacted twice with 10 ml of 10% dilute sulfuric acid at 50 °C for 0.5 h. The mixture was washed three times with the same ethanol / water mixture, filtered, and dried to obtain the porous organic polymer carrier POP-SO3H-2.

[0181] (2) Preparation of metallocene copolymerization catalysts:

[0182] 4.5 g of porous organic polymer support POP-SO3H-2 was vacuum filtered at 120 °C for 8 hours using a vacuum dryer. The treated POP-SO3H-2 support was added to a 250 ml nitrogen-purged reactor, along with 100 ml of dried toluene and 2.5 g of white MAO granules. The mixture was stirred at 25 °C for 1 hour, followed by the addition of 0.20 g of En(Ind)2HfCl2 (ethylene-bridged bis-indenyl hafnium dichloride) metallocene compound and 10 ml of toluene. The mixture was stirred for 0.5 hours and then reacted at 25 °C for 3 hours. After the reaction, the solvent was removed, and the mixture was dried to obtain the POP-SO3-MAO / Hf metallocene copolymer catalyst, denoted as Cat-M3. The Hf content in Cat-M3 was 32.7 μmol / g catalyst, and the aluminum content was 5.8 mmol / g catalyst.

[0183] Example 15

[0184] This embodiment provides a metallocene copolymerization catalyst, which is prepared by the following steps:

[0185] 4.5 g of porous organic polymer support POP-SO3H-2 was vacuum filtered at 120 °C for 8 hours using a vacuum dryer. The treated POP-SO3H-2 support was added to a 250 ml nitrogen-purged reactor, along with 100 ml of dried toluene and 2.5 g of white MAO granules. The mixture was stirred at 25 °C for 1 hour, followed by 0.16 g of (n-BuCp)2ZrCl2 (bis-n-butylcyclopentadienylzirconium dichloride) metallocene compound and 10 ml of toluene. The mixture was stirred for 0.5 hours and then reacted at 25 °C for 3 hours. After the reaction, the solvent was removed, and the mixture was dried to obtain the POP-SO3-MAO / Zr metallocene copolymer catalyst, denoted as Cat-M4. The catalyst Cat-M4 contained 28.2 μmol / g of Zr and 6.1 mmol / g of aluminum.

[0186] Example 16

[0187] This embodiment provides a metallocene copolymerization catalyst, which is prepared by the following steps:

[0188] 4.5 g of porous organic polymer support POP-SO3H-2 was vacuum filtered at 120 °C for 8 hours using a vacuum dryer. The treated support POP-SO3H-2 was added to a 250 ml nitrogen-purged reactor, along with 100 ml of dried toluene and 2.5 g of MAO white granules. The mixture was stirred at 25 °C for 1 hour, then 0.16 g of (1-Me-3-n-BuCp)2ZrCl2 [bis(1-methyl-3-n-butylcyclopentadienyl)zirconia dichloride] metallocene compound and 10 ml of toluene were added. The mixture was stirred for 0.5 hours and then reacted at 25 °C for 3 hours. After the reaction, the solvent was removed, and the mixture was dried to obtain a metallocene copolymer catalyst, designated Cat-M5. The catalyst Cat-M5 contained 34.3 μmol / g of Zr and 5.9 mmol / g of aluminum.

[0189] Evaluation of in-situ copolymerization of ethylene

[0190] Test Example 12-28

[0191] In a 2.0L dried ethylene oligomerization reactor, 1000ml of dried hexane, 2ml of triethylaluminum (TEAL) (1.0 mol / L), and 5ml of diethylaluminum chloride (1.0 mol / L) were added. The mixture was stirred for 3-5 minutes, and then a certain proportion of ethylene oligomerization catalysts Cat-1 to Cat-11 and metallocene copolymerization catalysts Cat-M1 to Cat-M5 were added. Ethylene was introduced, the temperature was raised to 80℃, and the reaction was carried out at a pressure of 1.0 MPa and a stirring speed of 600 rpm for 2 hours. After the reaction was completed, the mixture was cooled, filtered, and dried to obtain the polymer. The polymer particles had good morphology, and no adhesion to the polymerization reactor was observed. The catalyst dosage and polymer characteristics are shown in Table 2.

[0192] Table 2 Evaluation results and polymer characteristics of in-situ copolymerization of ethylene

[0193]

[0194]

[0195] In-situ copolymerization activity a Calculated using Zr / Hf ratio in zirconium or hafnium metallocene copolymer catalysts;

[0196] The ratio of oligomerization catalyst to metallocene catalyst is: the molar ratio of Zr in the ethylene oligomerization catalyst to M in the metallocene copolymerization catalyst.

[0197] The above in-situ copolymerization results show that the ethylene in-situ copolymerization catalyst system in this invention has good ethylene polymerization activity, which, calculated based on Zr or Hf metallocene active centers, can reach 28.4 × 10⁻⁶. 6The polymer exhibits good morphology, does not stick to the polymerization reactor, and the polyethylene density can be controlled between 0.89-0.93 g / ml.

Claims

1. An in-situ copolymerization catalyst system for ethylene, comprising an ethylene oligomerization catalyst, a metallocene copolymerization catalyst, and an organoaluminum compound; The ethylene oligomerization catalyst was prepared by supporting Zr compounds on an organic polymer support containing [SO2NCO] groups; The organic polymer carrier containing [SO2NCO] groups is prepared by copolymerization of monomers including divinylbenzene and functional monomers containing [SO2NCO] groups; wherein, 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. The metallocene copolymer catalyst is composed of an organic polymer support containing [SO3] groups, a metallocene compound, and a co-catalyst. The organic polymer carrier containing [SO3] groups is a copolymer of divinylbenzene and functional monomers containing [SO3] groups, which is formed by acidification. The functional monomers containing [SO3] groups include styrene containing sulfonic acid groups and / or olefins containing sulfonic acid groups.

2. The ethylene in-situ copolymerization catalyst system 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 ethylene in-situ copolymerization catalyst system 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-(allyl... One or more of the following: 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; And / or, the functional monomers containing the [SO3] group include sodium p-styrene sulfonate, p-styrene sulfonic acid, sodium m-styrene sulfonate, m-styrene sulfonic acid, o-styrene sulfonic acid, sodium o-styrene sulfonate, sodium 2-methyl-4-sulfonate styrene, 2-methyl-4-sulfonate styrene, sodium 2-methyl-3-sulfonate styrene, 2-methyl-3-sulfonate styrene, vinyl-4-methylbenzene sulfonic acid, sodium vinyl-4-methylbenzene sulfonate, sodium 2-ethyl-3-sulfonate styrene, 2-ethyl-3-sulfonate styrene, 4,4'-bis(2-sulfonate-styrene)-1,1'-biphenyl, 2-(2-Styryl)benzenesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate, propylene sulfonic acid, sodium propylene sulfonate, methpropylene sulfonic acid, sodium methpropylene sulfonate, 1-butenyl sulfonic acid, sodium 1-butenyl sulfonate, 1-pentenyl sulfonic acid, sodium 1-pentenyl sulfonate, 1-hexene sulfonic acid, sodium 1-hexene sulfonate, 1-heptene sulfonic acid, sodium 1-heptene sulfonate, 1-octenene sulfonic acid, sodium 1-octenene sulfonate, 2-ethanesulfonic acid methacrylate, sodium 2-ethanesulfonic acid methacrylate, 2-acrylamido-2-methyl-1-propane sulfonic acid, sodium allyl sulfonate, and one or more combinations of their hydrates.

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

5. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, Based on the mass of the organic polymer carrier containing the [SO3] group being 100%, the mass fraction of the functional monomer containing the [SO3] group is 5%-60%.

6. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, The general formula of the metallocene compound is Cp x MA y B z In this general formula, Cp is selected from unsubstituted cyclopentadienyl, substituted cyclopentadienyl, indenyl, fluorenyl, indenyl ligand in hydrogenated form or fluorenyl ligand in hydrogenated form, M is a group IVB transition metal element, A and B are each independently selected from halogen atom, hydrogen atom or alkyl, x is an integer from 1 to 3, and y and z are integers from 0 to 3; And / or, the cocatalyst is an alkylaluminoxane compound.

7. The ethylene in-situ copolymerization catalyst system according to claim 6, wherein, The metallocene compounds are selected from di(cyclopentadienyl)zirconia, di(cyclopentadienyl)dimethylzirconia, di(n-butylcyclopentadienyl)zirconia, di(n-butylcyclopentadienyl)dimethylzirconia, di(dimethylcyclopentadienyl)dimethylzirconia, diindylzirconia, methylene-bridged diindylzirconia, di(4,5,6,7-tetrahydro-1-indyl)zirconia, ethylidene-bridged di(indyl)zirconia, and dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)zirconia. Dimethylsilyl-bridged bis(2-methyl-4-phenylindenyl)dimethylzirconium, dimethylsilyl-bridged bis(2-methylindenyl)zirconium dichloride, dimethylsilyl-bridged bis(2-methyl-benzo[indenyl])zirconium dichloride, dimethylsilyl-bridged bis(2-methyl-benzo[indenyl])dimethylzirconium, dimethylsilyl-bridged bis(2-methylindenyl)dimethylzirconium, methylsilyl-bridged bis(2-methyl-4-phenylindenyl)dimethylzirconium, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)dimethylhafnium, bis(n-butyl) Hafnium dichloride (cyclopentadienyl), bis(n-butylcyclopentadienyl)dimethylhafnium, bis(dimethylcyclopentadienyl)dimethylhafnium, diindylhafnium dichloride, methylene-bridged diindylhafnium dichloride, bis(4,5,6,7-tetrahydro-1-indyl)hafnium dichloride, ethylidene-bridged bis(indyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)hafnium dichloride, dimethylsilyl-bridged bis(2-methyl-4-phenylindyl)dimethylhafnium, dimethylsilyl-bridged bis(2-methylindyl)dichloride Hafnium chloride, dimethylsilyl-bridged bis(2-methyl-benzo[indene]) difnium chloride, dimethylsilyl-bridged bis(2-methyl-benzo[indene]) dimethyl hafnium, dimethylsilyl-bridged bis(2-methyl-indene) dimethyl hafnium, methylsilyl-bridged bis(2-methyl-4-phenyl-indene) dimethyl hafnium, ethylene-bridged bis(indene) zirconium chloride, ethylene-bridged bis(indene) hafnium chloride, bis(n-butylcyclopentadienyl) zirconium chloride, and bis(1-methyl-3-n-butylcyclopentadienyl) zirconium chloride, or a combination of two or more thereof; And / or, the cocatalyst comprises methylaluminoxane.

8. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, In the ethylene oligomerization catalyst, the Zr content is from 50 micromoles of Zr / gram catalyst to 800 micromoles of Zr / gram catalyst.

9. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, In the metallocene copolymer catalyst, the co-catalyst is calculated as Al, and the metallocene compound is calculated as M. The molar ratio of co-catalyst to metallocene compound, Al:M, is 50-500. The co-catalyst, calculated as Al, has a content of 1 mmol / g catalyst to 12 mmol / g catalyst. The content of metal atoms M, the metal active center of the metallocene compound, is 5 μmol / g catalyst to 100 μmol / g catalyst.

10. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, The organoaluminum compound includes one or more of triethylaluminum, triisobutylaluminum, and diethylaluminum chloride.

11. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, The molar ratio of Al in the organoaluminum compound to Zr in the ethylene oligomerization catalyst is 1-500.

12. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, The molar ratio of Zr in the ethylene oligomerization catalyst to M in the metallocene copolymerization catalyst is 50:1 to 1:

10.

13. The ethylene in-situ copolymerization catalyst system according to claim 1, wherein, The preparation method of the ethylene oligomerization catalyst includes the following steps: (1) Preparation of organic polymer carriers containing [SO2NCO] groups: The carriers are prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization. The dispersion polymerization method is as follows: divinylbenzene and functional monomers containing [SO2NCO] groups are added to the dispersion solvent, then stabilizers and initiators are added, and the reaction is carried out at 50-80℃ for 5-12 hours. After washing, filtration and drying, the organic polymer carriers containing [SO2NCO] groups are obtained. (2) Zr compound loading: Zr compounds are loaded onto the organic polymer support containing [SO2NCO] groups obtained in step (1) using zirconium compound precursors to obtain the ethylene oligomerization catalyst; And / or, the preparation method of the metallocene copolymer catalyst includes the following steps: (a) Add divinylbenzene and the functional monomer containing the [SO3] group to a dispersion solvent consisting of a C1-C4 alcohol or a mixture of C1-C4 alcohol and water, dissolve the stabilizer in the system at 20-50°C, then add the initiator, heat to 60-80°C, react for 3-12 hours, and wash away impurities after the reaction is complete. (b) Add dilute acid and carry out an acidification reaction at 20-70℃. Wash and dry to obtain the organic polymer carrier containing [SO3] groups. (c) The organic polymer support containing [SO3] groups obtained in step (b) is added to an inert solvent under anhydrous and oxygen-free operating conditions, then a co-catalyst is added, and the reaction is carried out for 15-120 minutes. Then, a metallocene compound is added, the temperature is adjusted to -20°C to 40°C, and the reaction is carried out for 15-180 minutes. After washing with an inert solvent, the metallocene copolymer catalyst is obtained.

14. The ethylene in-situ copolymerization catalyst system according to claim 13, wherein, In the preparation method of the ethylene oligomerization catalyst, the reaction conditions of the dispersion polymerization method satisfy one or more of the following conditions (1)-condition (8), and step (2) satisfies the following conditions (10) and / or condition (11); The reaction conditions of the preparation method of the metallocene copolymer catalyst satisfy one or more of the following conditions (1)-condition (9); Condition (1): The dispersing solvent in step (1) includes one or more of alcohols, fatty acid ester solvents, and tetrahydrofuran; or, in the dispersing solvent of step (a), the C1-C4 alcohol includes one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol, and the mass ratio of C1-C4 alcohol to water in the C1-C4 alcohol-water mixture is 5-15:1; Condition (2): The mass ratio of the total amount of monomer added to the mass of the dispersing solvent is 1:5-20; Condition (3): The mass ratio of the functional monomer containing the [SO2NCO] group or the functional monomer containing the [SO3] group to the mass of divinylbenzene is 0.2-2:1; Condition (4): The stabilizer comprises polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer; Condition (5): The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-3:100; Condition (6): The initiator comprises azobisisobutyronitrile and / or benzoyl peroxide; Condition (7): The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:100; Condition (8): The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor; Condition (9): The dilute acid is dilute hydrochloric acid or dilute sulfuric acid; Condition (10): Step (2) of the preparation method of the ethylene oligomerization catalyst is to react the organic polymer support containing [SO2NCO] groups and the zirconium compound precursor in an organic solvent at 0-40°C for 1-5 h in equal amounts to obtain the ethylene selective oligomerization catalyst. Condition (11): The zirconium compound precursor includes one or more of zirconium tetrachloride, zirconium tetrachlorobistetrahydrofuranide, and chromium trihydrofuranide.

15. The ethylene in-situ copolymerization catalyst system according to claim 13, 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.

16. The application of the ethylene in-situ copolymerization catalyst system according to any one of claims 1-15 in ethylene polymerization, comprising the following steps: In a reaction vessel, a solvent, the ethylene oligomerization catalyst, the metallocene copolymerization catalyst, and the organoaluminum compound are added. Ethylene is then introduced, and the mixture is heated to react, yielding an in-situ ethylene copolymer.

17. The application according to claim 16, wherein, The ethylene polymerization temperature is 50-80℃ and the pressure is 0.1-3.0MPa.

18. The application according to claim 16, wherein, The density of polyethylene obtained by ethylene polymerization is 0.88-0.94 g / ml.

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